养猪废水及其处理系统中有机污染物的分布与去除
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摘要
近年来,养猪废水带来的环境污染问题越来越受到国内外学者的高度重视。由于其污染量大,处理过程不完全,已成为水环境的重要污染源。养猪废水主要来源于动物粪便、尿液及养殖场冲洗水。其有机物、固体悬浮物和氮磷的含量均高于我国《畜禽养殖业污染物排放标准》的几十甚至几百倍。养猪废水中有毒有害的有机物可分为传统污染物和新兴污染物,传统污染物比如类脂化合物包括油脂、脂肪酸和甾醇等,挥发性恶臭类化合物包括芳香族酚类化合物、含氮杂环化合物、挥发性脂肪酸和硫醇等；部分新兴污染物,如在养猪饲料中添加的兽药抗生素也同样在废水中检出。据调查,养猪过程中超量添加抗生素的现象十分普遍,我国每年有8万人直接死于滥用抗生素,而对猪的滥用要比人的情况严重百倍千倍,害死的猪不计其数。由于大多数养殖场处理设施不完善或不加以处理,这些污染物将直接排放到河流,湖泊及附近的水体中,造成环境水体的严重污染。
根据现有资料,关于养猪废水的研究课题多集中在传统污染物的分析上,如化学需氧量CODcr,生化需氧量BOD5,总氮TN和总磷TP等。废水中具有水质特征的特殊有机污染物却鲜有报道。本论文对养猪废水中有机物的特性和分布进行了全面解析,阐明了废水中溶解性有机物组分存在的差异,为探明其在处理过程中的降解行为提供了科学依据。同时对特殊污染物如恶臭类化合物和长链脂肪酸等的分析方法分别进行优化,并建立了废水中兽药抗生素的多残留检测方法。研究了在废水处理各环节污染物的去除效率,以及长期控制下的变化趋势。深入探讨了难降解大环内脂类抗生素的自然光降解过程,并充分利用获得的质谱信息对其降解产物进行一一鉴定,通过对原物质和产物的长期定量监测,模拟出自然条件下的降解趋势,为研究抗生素在自然环境中的迁移转化提供了理论和实践依据。论文的主要研究内容可以分为以下几个方面：
1.养猪废水及其处理系统中有机物的分布特征及去除效果
养猪废水水样来源于某种猪养殖场,废水经改进后的处理工艺净化后回用于农田。该处理工艺主要包括固液分离,酸化调节,厌氧发酵,仿生态自然氧化和快速渗滤等一系列措施。处理后的废水中污染物总量减少了90%以上,达到排放标准。由于养猪废水有机物成分差异大,为更全面地掌握其有机组成,我们采用三种典型的分组方法,将废水中的复杂有机物按照分子量不同,电荷特性不同及极性不同分成一系列结构、性质相对单一的物质组分,再根据其光谱及质谱特性进行研究。通过微滤及超滤技术将废水分成6种不同分子量的组分,M1(未经分离原水样),M2(小于1.0μm总组分),M3(小于0.45μm的溶解性组分),M4(介于0.45μm和1.0μm之间的微溶组分),M5(小于1 KDa的超滤液)和M6(介于1 KDa和0.45μm之间的胶体浓缩液)。经紫外光谱及特征性紫外吸收值SUVA分析,随着紫外吸收波长增大,组分SUVA吸收值具有一致的减小趋势：210 nm>254 nm> 280 nm.不同分子量组分的SUVA吸收值大小为：M5>M4>M6>M2>M3.各组分的红外吸收光谱具有相似性,都含有9条特征光谱带,但谱带强度略有不同。根据物质电荷特性不同,我们利用XAD-8树脂和阴阳离子交换树脂将可溶性有机物(DOM)组分(M3)进一步分成6个组分：憎水酸(HoA),憎水碱(HoB),憎水中性(HoN),亲水酸(HiA),亲水碱(HiB)和亲水中性(HiN)。通过紫外吸收光谱分析,在200nm至350nm紫外吸收区共有4条主要吸收光谱带,而重要的特征有机物光谱带产生在254 nm和280 nm。大部分有机物存在于憎水酸,憎水碱和亲水中性组分中。不同组分的红外吸收光谱差异很大,主要观测到9条光谱谱带,这与分子量组分测得的9条红外谱带并不完全一致。结果表明,废水中含有较高浓度的蛋白质和氨基酸,且P-H键的伸缩振动揭示了含磷化合物的存在。按照物质极性,我们将可溶性有机物(M3和M5)分成非极性、弱极性和极性三个不同组分。各组分样品经过富集、净化,气相色谱-质谱检测得出,主要的非极性组分以链状烷烃为主,从而推测出废水中含有的非极性可溶性有机物为碳链烷烃。在M3样品中,弱极性组分以芳香族酚类化合物为主,占到整个组分的一半以上。邻苯二甲酸酯(PAEs)和其它非极性脂类在M3样品中占整个组分的15%,而在样品M5中则占50%以上。在非烃类组分(即极性组分)中,甾醇和脂肪酸脂类占了整个组分的70%以上。同时,在非烃类组分中还检测出了6种药物的存在,这为废水中抗生素的研究提供了有用的信息。
2.恶臭类和长链脂肪酸类污染物在水处理系统中的分布与去除
恶臭类有机化合物的分布与去除：通过预处理条件的优化,顶空固相微萃取(HS-SPME)和固相萃取(SPE)两种富集方法的比较,建立了养猪废水中恶臭物质(4-甲基苯酚,4-乙基苯酚,吲哚和粪臭素)的测定方法。顶空固相微萃取采用PA萃取头,最佳萃取条件为：水样pH=4,离子强度为30%(氯化钠),恒温水浴温度70度,萃取时间30分钟,解析温度260度,解析时间3分钟。固相萃取采用Tenax吸附填料,自制固相萃取小柱,最佳萃取条件为：水样pH=7,离子强度为30%(氯化钠),样品过柱后,采用二氯甲烷和正己烷的混合溶液(1：2)作洗脱溶剂。采用最佳前处理条件,目标物的检出限范围在0.09μg L-1至1.48μg L-1之间,相对标准偏差低于15%。两种前处理方法在多项指标上进行了比较,比如方法的选择性,灵敏性和定量准确性等。结果表明,顶空固相微萃取法在最低定量检出限(LOQs)和精密度方面均优于固相萃取法。但固相萃取法因其操作简单、结果稳定的特点仍不失为有效的废水中半挥发性恶臭物质的定性定量测定方法。通过对不同处理出水中恶臭物质的组分分析,吲哚类恶臭化合物在生物处理过程中有部分去除,而酚类化合物降解效率低,不能有效去除。残留的毒性酚类化合物随出水排入到环境中将会给人类的健康带来危害。
长链脂肪酸化合物的分布与去除：采用XAD大孔树脂吸附,气相色谱质谱联用(GC-MS)检测技术,建立了养猪废水中不挥发中长链脂肪酸的测定方法。实验结果表明,废水中含有的主要脂肪酸(占所有脂肪酸的相对百分比)为棕榈酸(C16：0)和硬脂酸(C18：0)两种,同时也是自然界中最常见的长链脂肪酸。作为废水中含量最高的一种饱和酸,硬脂酸的浓度达到1.4 mg L-1.与此同时,部分一元不饱和脂肪酸,如(C16:1, C18:1和C20：1)在样品处理过程中也一并洗脱下来,并检测出较高浓度。脂肪酸在废水处理过程中有不同的表现行为,大部分脂肪酸在厌氧生物处理过程中没有有效的去除,而有近一半的脂肪酸在自然氧化过程中得到去除(出水W2),并在接下来的快速渗滤系统中基本完全去除(出水W3)。结果表明,此废水处理工艺对脂肪酸的去除效果显著。
3.兽药抗生素污染及去除效率研究
建立了地下水,湖水和养猪废水中多种兽药抗生素,如四环素(TCs),磺胺(SAs),喹诺酮(FQs)和氯霉素(CAPs)等的多残留检测方法。采用优化的固相萃取前处理技术结合液相色谱串联质谱检测仪器(SPE-LC/MS/MS)进行抗生素的痕量分析。同时,利用液相色谱飞行时间质谱仪(LC-ToF-MS)和LC-MS/MS两种仪器性能比较,建立了废水中8种青霉素(PCs)的快速检测方法。两种仪器都具有速度快,操作简单的优点。在青霉素的测定中,LC-MS/MS比LC-ToF-MS的检出限更低,准确性更高,因此优先考虑用于定量分析。同时对大环内脂类抗生素,如阿奇霉素,红霉素等采用已有方法进行分析。对四环素,磺胺,喹诺酮和氯霉素等的测定结果表明,夏季猪场地下水,附近湖水,养猪废水出水,进水中含有的抗生素浓度范围分别是1.6-8.6,5.7-11.6,7.9-1172.3和8.5-21692.7 ng L-1,冬季分别是2.0-7.3,6.7-11.7,5.8-409.5和32.8-11276.6 ng L-1.另外,阿莫西林,阿奇霉素和红霉素也同样在废水中检出,其浓度分别为540 ng L-1,602 ng L-1和456 ng L-1。所有样品(地下水、湖水、废水进、出水)的抗生素分析方法检出限均较低。虽然检测到的废水及环境水样中抗生素浓度均较低,它们残留在环境中对人类健康的危害和长期的毒性效应必须引起高度重视。
4.大环内脂类抗生素在水环境中光降解(模拟太阳光及自然光)过程研究
为探讨光降解去除大环内脂类抗生素阿奇霉素的可能性,从光降解动力学及光解产物的环境持续性效应角度进行了降解机理研究。分析了六种不同模拟水样对阿奇霉素的降解速率影响：高纯水(HPLC water),地表水(Freshwater, FW),加硝酸根的地表水(FW+nitrate),腐殖酸(Humic acids, HA),加硝酸根和腐殖酸的地表水(FW+nitrate+HA),养猪废水(piggerywastewater)。结果表明,阿奇霉素的光降解过程遵循一级反应动力学方程：FW+nitrate+HA> HA> piggery wastewater> FW+nitrate> FW> HPLC water。光降解过程产生了7种降解中间产物,利用超高压液相色谱与四极杆、飞行时间质谱联用仪在正离子模式下(UPLC-(+)ESI-QqToF-MS2)对可能的7种降解产物(TP1, TP2, TP3, TP4, TP5, TP6和TP 7)进行了鉴定。将测得的产物质量数和参考标准相对照,得到其精确质量数,并与软件提供的可能元素组成及饱和度相对比,结合原物质的化学结构推断出7种降解产物的结构式。结果表明,阿奇霉素的降解途径可归结为：产物1和产物2主要来源于阿奇霉素在不同糖环上丢失一个甲基所得,而产物3是在产物1的基础上去氧氨基糖环开环并脱氧所得,而产物4是产物2在另一糖环上又丢失一个甲基的结果。产物5和6来源于阿奇霉素分别丢掉去氧氨基糖和红霉糖,而产物7的组成为15环的大环内脂环,可能来源于产物1-6,也可能部分直接从产物1脱双糖而得。采用超高压液相色谱与四极杆串联质谱仪(UPLC-QqQ-MS2)在多反应监测模式下对7种产物的相对定量分析方法进行优化,得到7种产物的多反应监测方法。不同样品基质中的产物1-5基本都在光照1小时之内产生,并在连续照射10小时内达到最大浓度。而产物6和产物7的产生时间差异很大,其最大浓度都在照射30-50小时才获得。大多数降解产物在经过70小时照射后还未完全降解,特别是产物1和产物6在养猪废水基质中经100小时照射后还不能降解完全。因此,降解产物虽然产生迅速,但持续时间却相当长。为探索实际环境中抗生素的迁移转化规律,我们将阿奇霉素添加到采集的河水样品中,经自然光照射后得到阿奇霉素在自然条件下的环境行为。结果表明,阿奇霉素在自然光照射下也遵循一级动力学方程,且半衰期为5.4天,超过70%的阿奇霉素在8天的自然条件下被去除。然而,传统废水处理工艺的水力停留时间远远少于8天,这对阿奇霉素的去除是远远不够的。经过半天时间照射,产物1和产物6同时出现在河水样品中,经过35天的自然光照射也未能去除。可见,环境水体中的阿奇霉素在自然光照条件下的降解速率非常低,而其降解产物的环境持续时间相当长。阿奇霉素及其降解产物的环境毒性及存在风险应当引起人们的更多关注。研究此类抗生素污染物的迁移转化规律可以为环境风险评估提供理论依据。
As one of the most important environmental problems to be solved in many countries, piggery wastewater treatment and disposal raise a lot of attention in recent years. Piggery wastewater is a mixture of animal waste and flushing water, with high concentrations of organic matter, suspended solids, ammonia nitrogen and phosphorus, which far exceed the national discharging standards. Moreover, large numbers of toxic or harmful organic compounds existed in piggery wastewater, including conventional pollutants and emerging contaminants, such as lipoid substances including fats, fatty acid compounds and sterol, and odorants including aromatic phenols, nitrogen-containing heterocyclic compounds, volatile fatty acids, thiol, and two inorganic species, NH3 and H2S belong to the former. Some of the especially antibiotics which were belonged to emerging contaminants were also detected in piggery wastewater. These incomplete treated pollutants discharged into lakes, rivers or other water bodies, cause serious pollution of lakes and rivers.
According to the previous studies, most of the attention has been paid to the conventional pollutants analyses, such as COD, BOD5, TN and TP. The specific organic components of piggery wastewater are real studied. In the present study, the overall characterization of organic matters of piggery wastewater has been reported, the optimized quantification methods for conventional pollutants and emerging contaminants are well established respectively. Removal effectiveness of these pollutants during wastewater treatment plant in pig farm has been evaluated, paying a special attention to transformation and degradation fate of MLs antibiotics under solar irradiation. The main points of this thesis are summarized as follows:
Occurrence and removal of organic components in piggery wastewater. A new pilot-scale wastewater treatment plant containing preliminary treatment, RPAFR, MEOD and MFMI system was introduced. More than 90% pollutants were removed after treatment processes. Piggery wastewater was fractionated by three ways:different molecular size, resin absorption and polarity diversity. Different size fractions were operated by UF system into six parts from 1 kDa to 1μm: M1 (not fractionated), M2 (<1μm), M3 (<0.45μm), M4 (0.45μm～1μxm), M5 (<1 kDa) and M6 (1 kDa～0.45μm). The SUVA values at different wavelengths decreased with increase in UV absorbance:210 nm> 254 nm> 280 nm. The SUVA of different fractions changed in the following way:M5> M4> M6> M2> M3. The FT-IR spectra of organic matters of different fractions (M1-M6) were similar, and nine absorption bands were observed. DOM from sample M3 was fractionated into six fractions:HoA, HoB, HoN, HiA, HiB and HiN. From the UV spectra, the functional peaks appeared at 254 nm and 280 nm. Most of the organic matters were existed in HoA, HoN and HiB fractions. The FT-IR spectrum showed nine main bands. The existence of high concentration of protein and amino acids was revealed, and the P-H stretch was attributed to phosphorous substances. The main non-polar components were alkanes in both M3 and M5 fractions, indicating that non-polar organic pollutants were predominantly alkanes in the DOM fractions of the wastewater. For aromatic component, phenol-like compounds accounted for more than half of the aromatics fractions of organic compounds in sample M3, phthalates acid esters (PAEs) and other non-polar esters accounted for more than 15% of the aromatics compounds in sample M3, and more than 50% in sample M5. For non-hydrocarbons component, sterols and FAMEs accounted for more than 70% of the fractions. In this study, six pharmaceuticals were also identified in non-hydrocarbons fraction of M3 and M5.
Occurrence and removal of malodorous substances and long chain fatty acids. The analytical conditions of malodor substance which pre-concentrated by HS-SPME and SPE were optimized respectively. For HS-SPME, the optimal extraction conditions were pH=4,30 min at 70℃, with 30%(m/v) NaCl addition; the desorption process was 3 min at 260℃. For SPE, the best conditions were pH=7, with 30%(m/v) NaCl additon and 10 mL DCM-Hexane (1:2) as eluting solvent. At the best condition, the detection limits ranged from 0.09 to 1.48μg L-1 and the measurement precision was less than 15% of most compounds. The two methodologies were compared in evaluating indicators, such as selectivity, sensitivity and odor quantification. HS-SPME showed better results in terms of LOQs and RSD than SPE, but the semi-validated method of SPE also provide appropriate alternative approaches for qualitative and quantitative analysis of volatile compounds in piggery wastewater. All of the odorants were not completely removed in wastewater treatment plant, the residual toxicity of which was a incipient fault for human health.
The analytical method of long chain fatty acids determination is established by XAD resins separation coupled with GC-MS detection. The major fatty acids (considered as a relative percentage of the total) in the wastewater were palmitic acid (C16:0) and stearic acid (C18:0). Stearic acid achieved nearly 1.4 mg L-1 level in the wastewater as one of the saturated acid. Some unsaturated acids (C16:1,C18:1 and C20:1) were also coeluted and observed at relative high concentration. Most of the fatty acids were not well removed in RPAFR system. Nevertheless, more than half of the fatty acids were removed in MEOD system (effluent W2). Nearly all the fatty acids were completely removed after MFMI treatment (effluent W3). The obtained results showed that our pilot scale wastewater treatment process was suitable for fatty acids removal from piggery wastewater.
Occurrence and removal of veterinary antibiotics in wastewater treatment processes. An optimized SPE-LC/MS/MS method to analyze multi-residues of selected TCs, SAs, FQs and CAP in groundwater, lake water and swine wastewater was presented. A method for rapid multi-residue screening of PCs using LC-ToF-MS and LC-MS/MS were compared in this chapter. Both of LC-ToF-MS and LC-MS/MS were rapid and simple in PCs analysis, however, LC-MS/MS presented lower limit of detection and high reliability. The concentrations of antibiotics residues in groundwater, lake water, final effluent and influent swine wastewater were respectively 1.6-8.6, 5.7-11.6,7.9-1172.3 and 8.5-21692.7 ng L-1 in summer; and respectively 2.0-7.3,6.7-11.7, 5.8-409.5 and 32.8-11276.6 ng L-1 in winter. AMOX, AZT and ERT were appeared in relative low concentration in effluent wastewater (540 ng L-1,602 ng L-1 and 456 ng L-1, respectively). The LOQ levels were relative rather low in groundwater, lake water, final effluent wastewater and influent wastewater. Even though the antibiotics were detected at relatively low concentrations, there are high risks of their toxic effects on non-target organisms and, finally, on human health.
Photodegradation of macrolide antibiotics in the aquatic environment under simulated and natural sunlight irradiation. In order to explore the feasibility of photodegradation of macrolide antibiotics, the photodecomposition kinetics of AZT in six matrices (HPLC water, FW, FW+nitrate, HA, FW+nitrate+HA and piggery wastewater) were studied in photochemical reactor simulating solar irradiation. Photodegradation of AZT followed first-order kinetics in all six matrices with order of degradation rates as follows:FW+nitrate+HA> HA> piggery wastewater> FW+nitrate> FW> HPLC water. A UPLC-(+)ESI-QqToF-MS2 allowed to identify tentative major phototransformation products (TP 1, TP 2, TP 3, TP 4, TP 5, TP 6 and TP 7) of AZT was applied. TP 1 and TP 2 were generated by methyl radical loss from AZT. Further degradation of TP 1 and TP 2 leads to the generation of TP 3 and TP 4 via loss of·O·and methyl radical from two sugars, respectively, and then the formation of TP 5 and TP 6 by loss of desosamine and cladinose sugar from AZT, respectively, wile TP 5 and TP 6 could be degraded directly from AZT by sugar loss. The final product of TP 7 with macrolide ring was considered to be formatted from TP 1-TP 6 or directly from AZT. The optimized mass condition in MRM mode was used for TPs quantification by UPLC-QqQ-MS2. Most of the TP 1, TP 2, TP 3, TP 4 and TP 5 were generated less than 1 hour, and arrived at the highest concentration less than 10 hours in different matrices. While TP 6 and TP 7 were generated at very different time, and the highest concentrations were obtained between 30-50 hours irradiation. However, most of the TPs were detected in the final solution after 70 hours of irradiation. TP 1 and TP 6 persisted more than 100 hours in piggery wastewater under irradiation. The half life of AZT at 5.4 d in river water was obtained, and more than 70% of which was removed after 8 days. Transformation products of TP 1 and TP 6 appeared in half of one day in river water, and were also detected in the final sample under 35 days irradiation. Thus, the environmental risk of AZT and its degradation products need to be gained more attention, and the necessity of investigate the fate of these contaminants was evidenced in order to obtain a realistic estimation of the environmental impact.
根据现有资料,关于养猪废水的研究课题多集中在传统污染物的分析上,如化学需氧量CODcr,生化需氧量BOD5,总氮TN和总磷TP等。废水中具有水质特征的特殊有机污染物却鲜有报道。本论文对养猪废水中有机物的特性和分布进行了全面解析,阐明了废水中溶解性有机物组分存在的差异,为探明其在处理过程中的降解行为提供了科学依据。同时对特殊污染物如恶臭类化合物和长链脂肪酸等的分析方法分别进行优化,并建立了废水中兽药抗生素的多残留检测方法。研究了在废水处理各环节污染物的去除效率,以及长期控制下的变化趋势。深入探讨了难降解大环内脂类抗生素的自然光降解过程,并充分利用获得的质谱信息对其降解产物进行一一鉴定,通过对原物质和产物的长期定量监测,模拟出自然条件下的降解趋势,为研究抗生素在自然环境中的迁移转化提供了理论和实践依据。论文的主要研究内容可以分为以下几个方面：
1.养猪废水及其处理系统中有机物的分布特征及去除效果
养猪废水水样来源于某种猪养殖场,废水经改进后的处理工艺净化后回用于农田。该处理工艺主要包括固液分离,酸化调节,厌氧发酵,仿生态自然氧化和快速渗滤等一系列措施。处理后的废水中污染物总量减少了90%以上,达到排放标准。由于养猪废水有机物成分差异大,为更全面地掌握其有机组成,我们采用三种典型的分组方法,将废水中的复杂有机物按照分子量不同,电荷特性不同及极性不同分成一系列结构、性质相对单一的物质组分,再根据其光谱及质谱特性进行研究。通过微滤及超滤技术将废水分成6种不同分子量的组分,M1(未经分离原水样),M2(小于1.0μm总组分),M3(小于0.45μm的溶解性组分),M4(介于0.45μm和1.0μm之间的微溶组分),M5(小于1 KDa的超滤液)和M6(介于1 KDa和0.45μm之间的胶体浓缩液)。经紫外光谱及特征性紫外吸收值SUVA分析,随着紫外吸收波长增大,组分SUVA吸收值具有一致的减小趋势：210 nm>254 nm> 280 nm.不同分子量组分的SUVA吸收值大小为：M5>M4>M6>M2>M3.各组分的红外吸收光谱具有相似性,都含有9条特征光谱带,但谱带强度略有不同。根据物质电荷特性不同,我们利用XAD-8树脂和阴阳离子交换树脂将可溶性有机物(DOM)组分(M3)进一步分成6个组分：憎水酸(HoA),憎水碱(HoB),憎水中性(HoN),亲水酸(HiA),亲水碱(HiB)和亲水中性(HiN)。通过紫外吸收光谱分析,在200nm至350nm紫外吸收区共有4条主要吸收光谱带,而重要的特征有机物光谱带产生在254 nm和280 nm。大部分有机物存在于憎水酸,憎水碱和亲水中性组分中。不同组分的红外吸收光谱差异很大,主要观测到9条光谱谱带,这与分子量组分测得的9条红外谱带并不完全一致。结果表明,废水中含有较高浓度的蛋白质和氨基酸,且P-H键的伸缩振动揭示了含磷化合物的存在。按照物质极性,我们将可溶性有机物(M3和M5)分成非极性、弱极性和极性三个不同组分。各组分样品经过富集、净化,气相色谱-质谱检测得出,主要的非极性组分以链状烷烃为主,从而推测出废水中含有的非极性可溶性有机物为碳链烷烃。在M3样品中,弱极性组分以芳香族酚类化合物为主,占到整个组分的一半以上。邻苯二甲酸酯(PAEs)和其它非极性脂类在M3样品中占整个组分的15%,而在样品M5中则占50%以上。在非烃类组分(即极性组分)中,甾醇和脂肪酸脂类占了整个组分的70%以上。同时,在非烃类组分中还检测出了6种药物的存在,这为废水中抗生素的研究提供了有用的信息。
2.恶臭类和长链脂肪酸类污染物在水处理系统中的分布与去除
恶臭类有机化合物的分布与去除：通过预处理条件的优化,顶空固相微萃取(HS-SPME)和固相萃取(SPE)两种富集方法的比较,建立了养猪废水中恶臭物质(4-甲基苯酚,4-乙基苯酚,吲哚和粪臭素)的测定方法。顶空固相微萃取采用PA萃取头,最佳萃取条件为：水样pH=4,离子强度为30%(氯化钠),恒温水浴温度70度,萃取时间30分钟,解析温度260度,解析时间3分钟。固相萃取采用Tenax吸附填料,自制固相萃取小柱,最佳萃取条件为：水样pH=7,离子强度为30%(氯化钠),样品过柱后,采用二氯甲烷和正己烷的混合溶液(1：2)作洗脱溶剂。采用最佳前处理条件,目标物的检出限范围在0.09μg L-1至1.48μg L-1之间,相对标准偏差低于15%。两种前处理方法在多项指标上进行了比较,比如方法的选择性,灵敏性和定量准确性等。结果表明,顶空固相微萃取法在最低定量检出限(LOQs)和精密度方面均优于固相萃取法。但固相萃取法因其操作简单、结果稳定的特点仍不失为有效的废水中半挥发性恶臭物质的定性定量测定方法。通过对不同处理出水中恶臭物质的组分分析,吲哚类恶臭化合物在生物处理过程中有部分去除,而酚类化合物降解效率低,不能有效去除。残留的毒性酚类化合物随出水排入到环境中将会给人类的健康带来危害。
长链脂肪酸化合物的分布与去除：采用XAD大孔树脂吸附,气相色谱质谱联用(GC-MS)检测技术,建立了养猪废水中不挥发中长链脂肪酸的测定方法。实验结果表明,废水中含有的主要脂肪酸(占所有脂肪酸的相对百分比)为棕榈酸(C16：0)和硬脂酸(C18：0)两种,同时也是自然界中最常见的长链脂肪酸。作为废水中含量最高的一种饱和酸,硬脂酸的浓度达到1.4 mg L-1.与此同时,部分一元不饱和脂肪酸,如(C16:1, C18:1和C20：1)在样品处理过程中也一并洗脱下来,并检测出较高浓度。脂肪酸在废水处理过程中有不同的表现行为,大部分脂肪酸在厌氧生物处理过程中没有有效的去除,而有近一半的脂肪酸在自然氧化过程中得到去除(出水W2),并在接下来的快速渗滤系统中基本完全去除(出水W3)。结果表明,此废水处理工艺对脂肪酸的去除效果显著。
3.兽药抗生素污染及去除效率研究
建立了地下水,湖水和养猪废水中多种兽药抗生素,如四环素(TCs),磺胺(SAs),喹诺酮(FQs)和氯霉素(CAPs)等的多残留检测方法。采用优化的固相萃取前处理技术结合液相色谱串联质谱检测仪器(SPE-LC/MS/MS)进行抗生素的痕量分析。同时,利用液相色谱飞行时间质谱仪(LC-ToF-MS)和LC-MS/MS两种仪器性能比较,建立了废水中8种青霉素(PCs)的快速检测方法。两种仪器都具有速度快,操作简单的优点。在青霉素的测定中,LC-MS/MS比LC-ToF-MS的检出限更低,准确性更高,因此优先考虑用于定量分析。同时对大环内脂类抗生素,如阿奇霉素,红霉素等采用已有方法进行分析。对四环素,磺胺,喹诺酮和氯霉素等的测定结果表明,夏季猪场地下水,附近湖水,养猪废水出水,进水中含有的抗生素浓度范围分别是1.6-8.6,5.7-11.6,7.9-1172.3和8.5-21692.7 ng L-1,冬季分别是2.0-7.3,6.7-11.7,5.8-409.5和32.8-11276.6 ng L-1.另外,阿莫西林,阿奇霉素和红霉素也同样在废水中检出,其浓度分别为540 ng L-1,602 ng L-1和456 ng L-1。所有样品(地下水、湖水、废水进、出水)的抗生素分析方法检出限均较低。虽然检测到的废水及环境水样中抗生素浓度均较低,它们残留在环境中对人类健康的危害和长期的毒性效应必须引起高度重视。
4.大环内脂类抗生素在水环境中光降解(模拟太阳光及自然光)过程研究
为探讨光降解去除大环内脂类抗生素阿奇霉素的可能性,从光降解动力学及光解产物的环境持续性效应角度进行了降解机理研究。分析了六种不同模拟水样对阿奇霉素的降解速率影响：高纯水(HPLC water),地表水(Freshwater, FW),加硝酸根的地表水(FW+nitrate),腐殖酸(Humic acids, HA),加硝酸根和腐殖酸的地表水(FW+nitrate+HA),养猪废水(piggerywastewater)。结果表明,阿奇霉素的光降解过程遵循一级反应动力学方程：FW+nitrate+HA> HA> piggery wastewater> FW+nitrate> FW> HPLC water。光降解过程产生了7种降解中间产物,利用超高压液相色谱与四极杆、飞行时间质谱联用仪在正离子模式下(UPLC-(+)ESI-QqToF-MS2)对可能的7种降解产物(TP1, TP2, TP3, TP4, TP5, TP6和TP 7)进行了鉴定。将测得的产物质量数和参考标准相对照,得到其精确质量数,并与软件提供的可能元素组成及饱和度相对比,结合原物质的化学结构推断出7种降解产物的结构式。结果表明,阿奇霉素的降解途径可归结为：产物1和产物2主要来源于阿奇霉素在不同糖环上丢失一个甲基所得,而产物3是在产物1的基础上去氧氨基糖环开环并脱氧所得,而产物4是产物2在另一糖环上又丢失一个甲基的结果。产物5和6来源于阿奇霉素分别丢掉去氧氨基糖和红霉糖,而产物7的组成为15环的大环内脂环,可能来源于产物1-6,也可能部分直接从产物1脱双糖而得。采用超高压液相色谱与四极杆串联质谱仪(UPLC-QqQ-MS2)在多反应监测模式下对7种产物的相对定量分析方法进行优化,得到7种产物的多反应监测方法。不同样品基质中的产物1-5基本都在光照1小时之内产生,并在连续照射10小时内达到最大浓度。而产物6和产物7的产生时间差异很大,其最大浓度都在照射30-50小时才获得。大多数降解产物在经过70小时照射后还未完全降解,特别是产物1和产物6在养猪废水基质中经100小时照射后还不能降解完全。因此,降解产物虽然产生迅速,但持续时间却相当长。为探索实际环境中抗生素的迁移转化规律,我们将阿奇霉素添加到采集的河水样品中,经自然光照射后得到阿奇霉素在自然条件下的环境行为。结果表明,阿奇霉素在自然光照射下也遵循一级动力学方程,且半衰期为5.4天,超过70%的阿奇霉素在8天的自然条件下被去除。然而,传统废水处理工艺的水力停留时间远远少于8天,这对阿奇霉素的去除是远远不够的。经过半天时间照射,产物1和产物6同时出现在河水样品中,经过35天的自然光照射也未能去除。可见,环境水体中的阿奇霉素在自然光照条件下的降解速率非常低,而其降解产物的环境持续时间相当长。阿奇霉素及其降解产物的环境毒性及存在风险应当引起人们的更多关注。研究此类抗生素污染物的迁移转化规律可以为环境风险评估提供理论依据。
As one of the most important environmental problems to be solved in many countries, piggery wastewater treatment and disposal raise a lot of attention in recent years. Piggery wastewater is a mixture of animal waste and flushing water, with high concentrations of organic matter, suspended solids, ammonia nitrogen and phosphorus, which far exceed the national discharging standards. Moreover, large numbers of toxic or harmful organic compounds existed in piggery wastewater, including conventional pollutants and emerging contaminants, such as lipoid substances including fats, fatty acid compounds and sterol, and odorants including aromatic phenols, nitrogen-containing heterocyclic compounds, volatile fatty acids, thiol, and two inorganic species, NH3 and H2S belong to the former. Some of the especially antibiotics which were belonged to emerging contaminants were also detected in piggery wastewater. These incomplete treated pollutants discharged into lakes, rivers or other water bodies, cause serious pollution of lakes and rivers.
According to the previous studies, most of the attention has been paid to the conventional pollutants analyses, such as COD, BOD5, TN and TP. The specific organic components of piggery wastewater are real studied. In the present study, the overall characterization of organic matters of piggery wastewater has been reported, the optimized quantification methods for conventional pollutants and emerging contaminants are well established respectively. Removal effectiveness of these pollutants during wastewater treatment plant in pig farm has been evaluated, paying a special attention to transformation and degradation fate of MLs antibiotics under solar irradiation. The main points of this thesis are summarized as follows:
Occurrence and removal of organic components in piggery wastewater. A new pilot-scale wastewater treatment plant containing preliminary treatment, RPAFR, MEOD and MFMI system was introduced. More than 90% pollutants were removed after treatment processes. Piggery wastewater was fractionated by three ways:different molecular size, resin absorption and polarity diversity. Different size fractions were operated by UF system into six parts from 1 kDa to 1μm: M1 (not fractionated), M2 (<1μm), M3 (<0.45μm), M4 (0.45μm～1μxm), M5 (<1 kDa) and M6 (1 kDa～0.45μm). The SUVA values at different wavelengths decreased with increase in UV absorbance:210 nm> 254 nm> 280 nm. The SUVA of different fractions changed in the following way:M5> M4> M6> M2> M3. The FT-IR spectra of organic matters of different fractions (M1-M6) were similar, and nine absorption bands were observed. DOM from sample M3 was fractionated into six fractions:HoA, HoB, HoN, HiA, HiB and HiN. From the UV spectra, the functional peaks appeared at 254 nm and 280 nm. Most of the organic matters were existed in HoA, HoN and HiB fractions. The FT-IR spectrum showed nine main bands. The existence of high concentration of protein and amino acids was revealed, and the P-H stretch was attributed to phosphorous substances. The main non-polar components were alkanes in both M3 and M5 fractions, indicating that non-polar organic pollutants were predominantly alkanes in the DOM fractions of the wastewater. For aromatic component, phenol-like compounds accounted for more than half of the aromatics fractions of organic compounds in sample M3, phthalates acid esters (PAEs) and other non-polar esters accounted for more than 15% of the aromatics compounds in sample M3, and more than 50% in sample M5. For non-hydrocarbons component, sterols and FAMEs accounted for more than 70% of the fractions. In this study, six pharmaceuticals were also identified in non-hydrocarbons fraction of M3 and M5.
Occurrence and removal of malodorous substances and long chain fatty acids. The analytical conditions of malodor substance which pre-concentrated by HS-SPME and SPE were optimized respectively. For HS-SPME, the optimal extraction conditions were pH=4,30 min at 70℃, with 30%(m/v) NaCl addition; the desorption process was 3 min at 260℃. For SPE, the best conditions were pH=7, with 30%(m/v) NaCl additon and 10 mL DCM-Hexane (1:2) as eluting solvent. At the best condition, the detection limits ranged from 0.09 to 1.48μg L-1 and the measurement precision was less than 15% of most compounds. The two methodologies were compared in evaluating indicators, such as selectivity, sensitivity and odor quantification. HS-SPME showed better results in terms of LOQs and RSD than SPE, but the semi-validated method of SPE also provide appropriate alternative approaches for qualitative and quantitative analysis of volatile compounds in piggery wastewater. All of the odorants were not completely removed in wastewater treatment plant, the residual toxicity of which was a incipient fault for human health.
The analytical method of long chain fatty acids determination is established by XAD resins separation coupled with GC-MS detection. The major fatty acids (considered as a relative percentage of the total) in the wastewater were palmitic acid (C16:0) and stearic acid (C18:0). Stearic acid achieved nearly 1.4 mg L-1 level in the wastewater as one of the saturated acid. Some unsaturated acids (C16:1,C18:1 and C20:1) were also coeluted and observed at relative high concentration. Most of the fatty acids were not well removed in RPAFR system. Nevertheless, more than half of the fatty acids were removed in MEOD system (effluent W2). Nearly all the fatty acids were completely removed after MFMI treatment (effluent W3). The obtained results showed that our pilot scale wastewater treatment process was suitable for fatty acids removal from piggery wastewater.
Occurrence and removal of veterinary antibiotics in wastewater treatment processes. An optimized SPE-LC/MS/MS method to analyze multi-residues of selected TCs, SAs, FQs and CAP in groundwater, lake water and swine wastewater was presented. A method for rapid multi-residue screening of PCs using LC-ToF-MS and LC-MS/MS were compared in this chapter. Both of LC-ToF-MS and LC-MS/MS were rapid and simple in PCs analysis, however, LC-MS/MS presented lower limit of detection and high reliability. The concentrations of antibiotics residues in groundwater, lake water, final effluent and influent swine wastewater were respectively 1.6-8.6, 5.7-11.6,7.9-1172.3 and 8.5-21692.7 ng L-1 in summer; and respectively 2.0-7.3,6.7-11.7, 5.8-409.5 and 32.8-11276.6 ng L-1 in winter. AMOX, AZT and ERT were appeared in relative low concentration in effluent wastewater (540 ng L-1,602 ng L-1 and 456 ng L-1, respectively). The LOQ levels were relative rather low in groundwater, lake water, final effluent wastewater and influent wastewater. Even though the antibiotics were detected at relatively low concentrations, there are high risks of their toxic effects on non-target organisms and, finally, on human health.
Photodegradation of macrolide antibiotics in the aquatic environment under simulated and natural sunlight irradiation. In order to explore the feasibility of photodegradation of macrolide antibiotics, the photodecomposition kinetics of AZT in six matrices (HPLC water, FW, FW+nitrate, HA, FW+nitrate+HA and piggery wastewater) were studied in photochemical reactor simulating solar irradiation. Photodegradation of AZT followed first-order kinetics in all six matrices with order of degradation rates as follows:FW+nitrate+HA> HA> piggery wastewater> FW+nitrate> FW> HPLC water. A UPLC-(+)ESI-QqToF-MS2 allowed to identify tentative major phototransformation products (TP 1, TP 2, TP 3, TP 4, TP 5, TP 6 and TP 7) of AZT was applied. TP 1 and TP 2 were generated by methyl radical loss from AZT. Further degradation of TP 1 and TP 2 leads to the generation of TP 3 and TP 4 via loss of·O·and methyl radical from two sugars, respectively, and then the formation of TP 5 and TP 6 by loss of desosamine and cladinose sugar from AZT, respectively, wile TP 5 and TP 6 could be degraded directly from AZT by sugar loss. The final product of TP 7 with macrolide ring was considered to be formatted from TP 1-TP 6 or directly from AZT. The optimized mass condition in MRM mode was used for TPs quantification by UPLC-QqQ-MS2. Most of the TP 1, TP 2, TP 3, TP 4 and TP 5 were generated less than 1 hour, and arrived at the highest concentration less than 10 hours in different matrices. While TP 6 and TP 7 were generated at very different time, and the highest concentrations were obtained between 30-50 hours irradiation. However, most of the TPs were detected in the final solution after 70 hours of irradiation. TP 1 and TP 6 persisted more than 100 hours in piggery wastewater under irradiation. The half life of AZT at 5.4 d in river water was obtained, and more than 70% of which was removed after 8 days. Transformation products of TP 1 and TP 6 appeared in half of one day in river water, and were also detected in the final sample under 35 days irradiation. Thus, the environmental risk of AZT and its degradation products need to be gained more attention, and the necessity of investigate the fate of these contaminants was evidenced in order to obtain a realistic estimation of the environmental impact.
引文
[1]Cassel E A, Warner A F, and Jacobs G B. De-watering chicken manures by vacuum filtration. in In proceedings, national symposium on management of farm animal wastes.1966. michigan state university:A. S. A. E.
[2]Wang k, Livestock and Poultry Pollution Prevention Technology and Policy.6.2004:Chemical Industry Press.
[3]Tong L, Li P, Wang Y, et al., Analysis of veterinary antibiotic residues in swine wastewater and environmental water samples using optimized SPE-LC/MS/MS. Chemosphere 2009.74: 1090-1097.
[4]Ji M and Wu C, The harmful to the environment and the pre-release measures for intensive farming. Environmental Science & Technology 1999(2):32-32.
[5]Andara A R and Esteban J M L, Transition of particle size fractions in anaerobic digestion of the solid fraction of piggery manure. Biomass Bioenerg.2002.23:229-235.
[6]Sanchez E, Borja R, Travieso L, et al., Effect of organic loading rate on the stability, operational parameters and performance of a secondary upflow anaerobic sludge bed reactor treating piggery waste. Bioresour. Technol.2005.96:335-344.
[7]Torre A I D 1, Jimenez J A, Carballo M, et al., Ecotoxicological evaluation of pig slurry. Chemosphere 2000.41:1629-1635.
[8]Zhang H, Qu J, Liu H, et al., Isolation of dissolved organic matter in effluents from sewage treatment plant and evaluation of the influences on its DBPs formation. Separation and Purification Technology 2008.64:31-37.
[9]Levine A, Cripps S, and Lawler D. Benefits of particle size management for biological wastewater treatment.. in ASCE proceedings of the national conference on environmental engineering.1985. Boston, USA.
[10]Olboter L and Vogelpohl A, Influence of particle size distribution on the dewatering of organic sludges. Water Science and Technology 1993.28(1):149-157.
[11]Andara A and Esteban J M L, Transition of particle size fractions in anaerobic digestion of the solid fraction of piggery manure. Biomass & Bioenergy 2002.23:229-235.
[12]Seo D, Kim Y, Ham S, et al., Characterization of dissolved organic matter in leachate discharged from final disposal sites which contained municipal solid waste incineration residues. J. Hazard Mater.2007.148:679-692.
[13]Shon H, Vigneswaran S, Kim I S, et al., Fouling of ultrafiltration membrane by effluent organic matter:A detailed characterization using different organic fractions in wastewater. J. Membr. Sci.2006.278:232-238.
[14]Liu R X, Lead J R, and Baker A, Fluorescence characterization of cross flow ultrafiltration derived freshwater colloidal and dissolved organic matter. Chemosphere 2007.68:1304-1311.
[15]Her N, Amy G, Chung J W, et al., Characterizing dissolved organic matter and evaluating associated nanofiltration membrane fouling. Chemosphere 2008.70:495-502.
[16]Santos P, Otero M, Duarte R M B, et al, Spectroscopic characterization of dissolved organic matter isolated from rainwater. Chemosphere 2009.74:1053-1061.
[17]Leenheer J A, Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and wastewaters. Environmental Science & Technology 1981. 15:578-587.
[18]Imai A, Fukushima T, Matsushige K, et al., Characterization of dissolved organic matter in effluents from wastewater treatment plants. Water Research 2002.36:859-870.
[19]Jouraiphy A, Amir S, Winterton P, et al., Structural study of the fulvic fraction during composting of activated sludge-plant matter:Elemental analysis, FTIR and 13-C NMR. Bioresour. Technol.2008.99:1066-1072.
[20]Zhang T, Lu J F, Ma J, et al., Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation. Chemosphere 2008.71: 911-921.
[21]Ferrer I, Barber L B, and Thurman M, Gas chromatographic-mass spectrometric fragmentation study of phytoestrogens as their trimethylsilyl derivatives:identification in soy milk and wastewater samples. J. Chromatogr. A 2009.32:6024-6032.
[22]Lu F, Chang C H, Lee D J, et al., Dissolved organic matter with multi-peak fluorophores in landfill leachate. Chemosphere 2009.74:575-582.
[23]Baker A and Spencer R G M, Characterization of dissolved organic matter from source to sea using fluorescence and absorbance spectroscopy. Sci. Total Environ.2004.333:217-232.
[24]Chen J, LeBoef E J, Dai S, et al., Fluorescence spectroscopic studies of natural organic matter fractions. Chemosphere 2003.50:639-647.
[25]Park J-H, Spectroscopic characterization of dissolved organic matter and its interactions with metals in surface waters using size exclusion chromatography. Chemosphere 2009.4:485-494.
[26]Saadi I, Borisover M, Armon R, et al., Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements. Chemosphere 2006.63:530-539.
[27]Cai L, Koziel J A, Lo Y, et al., Characterization of volatile organic compounds and odorants associated with swine barn particulate matter using solid-phase microextraction and gas
chromatography-mass spectrometry-olfactometry. Journal of Chromatography A 2006.1102: 60-72.
[28]Schiffman S S, Bennett J L, and Raymer J H, Quantification of odors and odorants from swine operations in North Carolina. Agricultural and Forest Meteorology 2001.108:213-240.
[29]Thiebaut B, Lattuati-Derieux A, Hocevar M, et al., Application of headspace SPME-GC-MS in characterisation of odorous volatile organic compounds emitted from magnetic tape coatings based on poly (urethane-ester) after natural and artificial ageing. Polymer testing 2007.26: 243-256.
[30]Larreta J, Vallejo A, Bilbao U, et al., Experimental design to optimise the analysis of organic volatile compounds in cow slurry by headspace solid-phase microextraction-gas chromatography-mass spectrometry. Journal of Chromatography A 2006.1136:1-9.
[31]Zhu J, Areview of microbiology in swine manure odor control. Agriculture, Ecosystems and Environment 2000.78:93-106
[32]EPA, Phenols by Gas Chromatography:Capillary Column Technique, Environmental Protection Agency W, DC, Editor.1995. p.1.
[33]Dai C, Zeng K, Duan Y, et al., Treatment of fatty acid-containing wastewate. Industrial water & wastewater 2007.38(1):47-50.
[34]Brondz I, Development of fatty acid analysis by high-performance liquid chromatography, gas chromatography, and related techniques. Analytica Chimica Acta 2002.465:1-37.
[35]Pan L, Adams M, and Pawliszyn J, Determination of Fatty Acids Using Solid-Phase Microextraction. Analytical Chemistry 1995.67:4396-4403.
[36]Managaki S, Murate A, Takada H, et al., Distribution of macrolides, sulfonamides, and trimethoprim in tropical waters:ubiquitous occurrence of veterinary antibiotics in the Mekong Delta.. Environmental Science and Technology 2007.41:8004-8010.
[37]Alban L, Nielsen E, and Dahl J, A human health risk assessment for macrolide-resistant Campylobacter associated with the use of macrolides in Danish pig production. Prev. Vet. Med. 2008.83:115-129.
[38]FDA, New guidance for industry on antimicrobial drugs for food animals., Administration U Fa D, Editor.2003. p.35.
[39]Sarmah A K, Meyer M T, and Boxall A B A, A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment. Chemosphere 2006.65:725-759.
[40]Malintan N T and Mohd M A, Determination of sulfonamides in selected Malaysian swine wastewater by high-performance liquid chromatography. Journal of Chromatography A 2006.1127: 154-160.
[41]Nakata H, Kannan K, Jones P D, et al., Determination of Fluoroquinolone antibiotics in wastewater effluents by liquid chromatography mass spectrometry and fluorescence detection. Chemosphere 2005.58:759-766.
[42]Kemper N, Veterinary antibiotics in the aquatic and terrestrial environment. Ecological Indicators 2008.8:1-13.
[43]Hernandez F, Sancho J V, Ibanez M, et al., Antibiotic residue determination in environmental waters by LC-MS. Trends in Analytical Chemistry 2007.26(6):466-485.
[44]Diaz-Cruz M S, Garca-Galan M J, and Barcelo D, Highly sensitive simultaneous determination of sulfonamide antibiotics and one metabolite in environmental waters by liquid chromatography-quadrupole linear ion trap-mass spectrometry. Journal of Chromatography A 2008. 1193:50-59.
[45]Pierini E, Famiglini G, Mangani F, et al., Fate of Enrofloxacin in Swine Sewage. J. Agric. Food Chem.2004.52:3473-3477.
[46]Vieno N M, Tuhkanen T, and Kronberg L, Analysis of neutral and basic pharmaceuticals in sewage treatment plants and in recipient rivers using solid phase extraction and liquid chromatography-tandem mass spectrometry detection. Journal of Chromatography A 2006.1134: 101-111.
[47]Mcardell C S, Molnar E, Suter M J F, et al., Occurrence and fate of macrolide antibiotics in wastewater treatment plants and in the glatt valley watershed, Switzerland. Environmental Science & Technology 2003.37(24):5479-5486.
[48]Kummerer K, Antibiotics in the aquatic environment-A review. Chemosphere 2009.75(4): 417-441.
[49]Diaz-Cruz M S, Llorca M, and Barcelo D, Organic UV filters and their photodegradates, metabolites and disinfection by-products in the aquatic environment. Trends in Analytical Chemistry 2008.27(10):873-887.
[50]Deng L, Zheng P, Chen Z, et al., Improvement in post-treatment of digested swine wastewater. Bioresource Technology 2008.99:3136-3145.
[51]Weiland P, Anaerobic waste digestion in Germany-Status and recent developments. Biodegradation 2000(11):415-421.
[52]Ngoddy P O, Harper J P, and Gerrish J B, Enhanced treatment of livestock wastewater. J.agric.Engng. Res.1974.19:313-326.
[53]Glerum J C, Klomp G, and Poelma H R. The separation of solid and liquid parts of pig slurry. in In proceedings, international symposium on livestock wastes.1971. Ohio state university center.
[54]Lo K V, Liao P H, and Gao Y C, Anaerobic treatment of swine wastewater using hybrid UASB reactors. Bioresource Technology 1994.47:153-157.
[55]Deng L, Cai C, and Chen Z, The treatment of pig slurry by a full-scale anaerobic-adding raw wastewater-Intermittent aeration process. Biosystems Engineering 2007.98:327-334.
[56]Vanotti M B, Szogi A A, Hunt P G, et al., Development of environmentally superior treatment system to replace anaerobic swine lagoons in the USA. Bioresource Technology 2007.98: 3184-3194.
[57]Deng L, Zheng P, and Chen Z, Anaerobic digestion and post-treatment of swinewastewater using IC-SBR process with bypass of raw wastewate. Process Biochemistry 2006.41:965-969.
[58]Bortone G, Integrated anaerobic/aerobic biological treatment for intensive swine production. Bioresource Technology 2009.100(22):5424-5430.
[59]Edgerton B D, McNevin D, Wong C H, et al., Strategies for dealing with piggery effluent in Australia:the sequencing batch reactor as a solution. Water Science and Technology 1999.41(1): 123-126.
[60]Evans M R and Deans E A, The effect of temperature and residence time on aerobic treatment of pig slurry. Agricultural Wastes 1983(5):25-36.
[61]Zhu J, Areview of microbiology in swine manure odor control. Agr. Ecosystem Environ.2000. 78:93-106.
[62]Alaya S B, Haouech L, Cherif H, et al., Aeration management in an oxidation ditch. Desalination 2010.252(1-3):172-178.
[63]Hussain S, Aziz H A, Isa M H, et al., Physico-chemical method for ammonia removal from synthetic wastewater using limestone and GAC in batch and column studies. Bioresource Technology 2006.98:874-880.
[64]Hencha K R, Bissonnette G K, Sexstone A J, et al., Fate of physical, chemical, and microbial contaminants in domestic wastewater followingtreatment by small constructed wetlands. Water Research 2003.37:921-927.
[65]Wang Y F, Lin F, and Pang W Q, Ammonium exchange in aqueous solution using Chinese natural clinoptilolite and modifed zeolite. Journal of Hazardous Materials 2007.142:160-164.
[66]Rodgers M, Healy M G, and Mulqueen J, Organic carbon removal and nitrification of high strength wastewaters using stratified sand filters. Water Research 2005.39:3279-3286.
[67]APHA A P H A, Standard methods for the examination of water and wastewater,20th ed, APHA W, AWWA, Washington, D.C, USA, Editor.1998.
[68]Zhang H, Qu J, Liu H, et al., Characterization of isolated fractions of dissolved organic matter from sewage treatment plant and the related disinfection by-products formation potential. Journal of Hazardous Materials 2009.164:1433-1438.
[69]Obaja D, Mace S, and Mata-Alvarez J, Biological nutrient removal by a sequencing batch reactor (SBR) using an internal organic carbon source in digested piggery wastewater. Bioresour. Technol.2005.96:7-14.
[70]Bernet N, Delgenes N, Akunna J C, et al., Combined anaerobic-aerobic SBR for the treatment of piggery wastewater. Water Research 2000.34:611-619.
[71]Huo S, Xi B, Yu H, et al., Characteristics of dissolved organic matter (DOM) in leachate with different landfill ages. Journal of Environmental Sciences 2008.20:492-498.
[72]Her N, Amy G, McKnight D, et al., Characterization of DOM as a function of MW by fluorescence EEM and HPLC-SEC using UVA, DOC, and fluorescence detection. Water Research 2003.37:4295-4303.
[73]HAO R, CAO K, ZHAO G, et al., Ultraviolet Absorption Spectrum Characterization Approach for Quantitative Analysis of Dissolved Organic Contaminants in Sewag. Journal of Beijing University of Technology 2006.32(12):1062-1066.
[74]Ou Y, Lou Z, and Zhao Y, On relationship between COD values in leachate and their UV absorbance in various conditions. Journal of University of Science and Technology of Suzhou (Engineering and Technology) 2003.16(3):6-10.
[75]Lguirati A, Baddi G A, Mousadik A E, et al., Analysis of humic acids from aerated and non-aerated urban landfill composts. International Biodeterioration & Biodegradation 2005.56: 8-16.
[76]Rappert S and Muller R, Odor compounds in waste gas emissions from agricultural operations and food industries. Waste Manage.2005.25:887-907.
[77]Jensen M T, Cox R P, and Jensen B B,3-Methylindole (skatole) and indole production by mixed populations of pig fecal bacteria. Applied and Environment Microbiology 1995.61: 3180-3184.
[78]Boursier H, Beline F, and Paul. E, Piggery wastewater characterisation for biological nitrogen removal process design. Bioresource Technology 2005.96:351-358.
[79]Kaiser J P, Feng Y, and Bollag. J M, Microbial metabolism of pyridine, quinoline, acridine, and their derivatives under aerobic and anaerobic conditions. Microbiology Review 1996.60: 483-498.
[80]Zhang Z and Zhu J, Effectiveness of short-term aeration in treating swine finishing manure to reduce odor generation potential. Agriculture Ecosystems & Environment 2005.105:115-125.
[81]Lim T T, Heber A J, Ni J, et al., Odor and gas release from anaerobic treatment lagoons for swine manure. Journal of Environmental Quality 2003.32:406-416.
[82]Werker A G, Jennifer Becker, and Carly Huitema, Assessment of activated sludge microbial community analysis in full-scale biological wastewater treatment plants using patterns of fatty acid isopropyl esters (FAPEs). Water research 2003.37:2162-2172.
[83]Vedrenne F, Beline F, Dabert P, et al., The effect of incubation conditions on the laboratory measurement of the methane producing capacity of livestock wastes. Bioresource Technology 2008.99:146-155.
[84]Wong B, Show K, Su A, et al., Effect of volatile fatty acid composition on upflow anaerobic sludge blanket (UASB) performance. Energy Fuels 2008.22:108-112.
[85]Li Y, Gu G, Zhao J, et al., Anoxic degradation of nitrogenous heterocyclic compounds by acclimated activated sludge. Process Biochemistry 2001.37:81-86.
[86]Deslandes B, Gariepy C, and Houde A, Review of microbiological and biochemical effects of skatole on animal production. Livestock Production Science 2001.71:193-200.
[87]Zhu J, A review of microbiology in swine manure odor control. Agriculture Ecosystems & Environment 2001.78:93-106.
[88]Willig S, Lacorn M, and Claus R, Development of a rapid and accurate method for the determination of key compounds of pig odor. Journal of Chromatography A 2004.1038:11-18.
[89]Stashenko E E and Martinez J R, Derivatization and solid-phase microextraction. Trends in Analytical Chemistry 2004.23:553-561.
[90]Demeestere K, Dewulf J, Witte B, et al., Sample preparation for the analysis of volatile organic compounds in air and water matrices. Journal of Chromatography A 2007.1153:130-144.
[91]Romero J and Ventura F, Identification of 1,3-dioxanes and 1,3-dioxolanes as malodorous compounds at trace levels in river water, groundwater, and tap water.. Environmental Science & Technology 1998.32:206-216.
[92]Babol J, Squires E J, and Lundstrom K, Relationship between metabolism of androstenone and skatole in intact male pigs. Journal of Animal Science 1999.77:84-92.
[93]Zhou F, Li X, and Zeng Z, Determination of phenolic compounds in wastewater samples using a novel fiber by solid-phase microextraction coupled to gas chromatography. Analytica Chimica Acta 2005.538:63-70.
[94]Akesson-Nilsson G, Isolation of chlorinated fatty acid methyl esters derived from cell-culture medium and from fish lipids by using an aminopropyl solid-phase extraction column. Journal of Chromatography A 2003.996:173-180.
[95]Bagheri H and Saraji M, Conductive polymers as new media for solid-phase extraction: Isolation of chlorophenols from water sample. Journal of Chromatography A 2003.986:111-119.
[96]Polo M, Llompart M, Garcia-Jares C, et al., Development of a solid-phase microextraction method for the analysis of phenolic flame retardants in water samples. Journal of Chromatography A 2006.1124:11-21.
[97]Ballesteros-Gomez A, Rubio S, and Perez-Bendito D, Analytical methods for the determination of bisphenol A in food. Journal of Chromatography A 2009.1216:449-469.
[98]Loughrin J H, Comparison of solid-phase microextraction and stir bar sorptive extraction for the quantification of malodors in wastewater. Journal of Agricultural and Food Chemistry 2006.54: 3237-3241.
[99]Insa S, Besalu E, Iglesias C, et al., Ethanol/water extraction combined with solid-phase extraction and solid-phase microextraction concentration for the determination of chlorophenols in cork stoppers. Journal of Agricultural and Food Chemistry 2006.54:627-632.
[100]Olejniczak J and Staniewski J, Enrichment of phenols from water with in-situ derivatization by in-tube solid phase microextraction-solvent desorption prior to off-line gas chromatographic determination with large-volume injection. Journal of Analytica Chimica Acta 2007.588:64-72.
[101]Serrano E, Beltran J, and Hernandez F, Application of multiple headspace-solid-phase microextraction followed by gas chromatography-mass spectrometry to quantitative analysis of tomato aroma components. Journal of Chromatography A 2009.1216:127-133.
[102]Mardones C, Baer D, Silva J, et al., Determination of halophenolic wood preservant traces in milk using headspace solid-phase microextraction and gas chromatography-mass spectrometry. journal of Chromatography A 2008.1215:1-7.
[103]Stalikas C, Fiamegos Y, Sakkas V, et al., Developments on chemometric approaches to optimize and evaluate microextraction. Journal of Chromatography A 2009.1216:175-189.
[104]Nome R C and Carasek E, Comparative study of the use of flow through systems with and without air segmentation for determination of phenols by solid-phase microextraction-gas chromatography. Journal of Chromatography A 2004.59:387-391.
[105]Mejias R C, Mann R N, Moreno V G, et al., Optimisation of headspace solid-phase microextraction for the analysis of volatile phenols in wine. Journal of Chromatography A 2003. 995:11-20.
[106]Canosa P, Rodriguez I, Rubi E, et al., Optimization of solid-phase microextraction conditions for the determination of triclosan and possible related compounds in water samples. Journal of Chromatography A 2005.1072:107-115.
[107]Vinas P, Campillo N, Martinez-Castillo N, et al., Solid-phase microextraction on-fiber derivatization for the analysis of some polyphenols in wine and grapes using gas chromatography-mass spectrometry. journal of Chromatography A 2009.1216:1279-1284.
[108]Silva I, Rocha S M, and Coimbra M A, Headspace solid phase microextraction and gas chromatography-quadrupole ass spectrometry methodology for analysis of volatile compounds of marine alt as potential origin biomarkers. Analytica Chimica Acta 2009.635:167-174.
[109]Wait A D, Evolution of Organic Analytical Methods in Environmental Forensic Chemistry. Environmental Forensics 2000.1:37-46.
[110]Werker A G and Hall E R, Development and application of a fatty acid based microbial community structure similarity index. Environmetrics 2002.13:347-363.
[111]Werker A G, Applied microbial ecology for the control of wastewater treatment systems. Water 21, IWA 2001.13:38-42.
[112]Kornel Nagy, Annamaria Jakab, Jeno Fekete, et al., An HPLC-MS approach for analysis of very long chain fatty acids and other apolar compounds on octadecyl-silica phase using partly miscible solvents. Analytical Chemistry 2004.76:1935-1941.
[113]Thurnhofer S and Vetter W, A gas chromatography/electron ionization-mass spectrometry-selected ion monitoring method for determining the fatty acid pattern in food after formation of fatty acid methyl esters. Journal of Agricultural and Food Chemistry 2005.53: 8896-8903.
[114]Jalali-Heravi M and Vosough M, Characterization and determination of fatty acids in fish oil using gas chromatography-mass spectrometry coupled with chemometric resolution techniques. Journal of Chromatography A 2004.1024:165-176.
[115]Lin P, Marc A, and Janusz P, Determination of fatty acids using solid-phase microextraction. Analytical Chemistry 1995.67:4396-4403.
[116]Martin D, Antequera T, Gonzalez E, et al., Changes in the fatty acid profile of the subcutaneous fat of swine throughout fattening as affected by dietary conjugated linoleic acid and monounsaturated fatty acids. J. Agric. Food Chem 2007.55:10820-10826.
[117]Christian T, Schneider R J, Farber H A, et al., Determination of antibiotics residues in manure, soil, and surface waters. Acta Hydroch. Hydrobiol.2003.31:34-44.
[118]Giger W, Alder A C, Golet E M, et al., Occurrence and fate of antibiotics as trace contaminants in wastewaters sewage sludge and surface waters. Chimia 2003.57:485-491.
[119]Martinez-Carballo E, Gonzalez-Barreiro C, Scharf S, et al., Environmental monitoring study of selected veterinary antibiotics in animal manure and soils in Austria. Environ Pollut.2007.148: 570-579.
[120]Batt A L, Snow D D, and Aga D S, Occurrence of sulfonamide antimicrobials in private water wells in Washington County, Idaho, USA. Chemosphere 2006.64:1963-1971.
[121]Gros M, Petrovic M, and Damia B, Development of a multi-residue analytical methodology based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 2006.70:678-690.
[122]Managaki S, Murate A, Takada H, et al., Distribution of macrolides, sulfonamides, and trimethoprim in tropical waters:ubiquitous occurrence of veterinary antibiotics in the Mekong Delta. Environ. Sci. Technol.2007.41:8004-8010.
[123]Jemal M, Schuster A, and Whigan D B, Liquid chromatography/tandem mass spectrometry methods for quantification of mevalonic acid in human plasma and urine:method validation, demonstration of using a surrogate standard, and demonstration of unacceptable matrix e□ect in spite of use of a stable isotope analog internal standard. Rapid Commun. Mass Spectrom.2003.17: 1723-1734.
[124]Lindberg R, Jarnheimer P, Olsen B, et al., Determination of antibiotic substances in hospital sewage water using solid phase extraction and liquid chromatography/mass spectrometry and group analogue internal standards. Chemosphere 2004.57:1479-1488.
[125]Castiglioni S, Bagnati R, Fanelli R, et al., Removal of pharmaceuticals in sewage treatment plants in Italy. Environ. Sci. Technol.2006.40:357-363.
[126]Gomez M J, Petrovic M, Fernandez-Alba A R, et al., Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography-tandem mass spectrometry analysis in hospital effluent wastewaters. Journal of Chromatography A 2006.1114: 224-233.
[127]Lucchetti D, Fabrizi L, Esposito A, et al., Simple confirmatory method for the determination of erythromycin residues in trout:a fast liquid-liquid extraction followed by liquid chromatography-tandem mass spectrometry. J. Agric. Food Chem 2005.53:9689-9694.
[128]Kay P, Blackwell P A, and Boxall A B A, Column studies to investigate the fate of veterinary antibiotics in clay soils following slurry application to agricultural land. Chemosphere 2005.60: 497-507.
[129]Schubert J K, Miekisch W, Fuchs P, et al., Determination of antibiotic drug concentrations in circulating human blood by means of solid phase micro-extraction. Clin. Chim. Acta 2007.386: 57-62.
[130]Golet E M, Alder A C, Hartmann A, et al., Trace determination of fluoroquinolone antibacterial agents in urban wastewater by solid-phase extraction and liquid chromatography with fluorescence detection. Analytical Chemistry 2001.73:3632-3638.
[131]Vieno N, Tuhkanen T, and Kronberg L, Elimination of pharmaceuticals in sewage treatment plants in Finland, water research 2007.41:1001-1012.
[132]Connor S and Aga D S, Analysis of tetracycline antibiotics in soil:Advances in extraction, clean-up, and quantification. Trends in Analytical Chemistry 2007.26:456-465.
[133]Gros M, Petrovic M, and Damia B, Tracing Pharmaceutical Residues of Different Therapeutic Classes in Environmental Waters by Using Liquid Chromatography/Quadrupole-Linear Ion Trap Mass Spectrometry and Automated Library Searching. Analytical Chemistry 2009.81:898-912.
[134]Kim S, Eichhorn P, Jensen J N, et al., Removal of antibiotics in wastewater:effect of hydraulic and solid retention times on the fate of tetracycline in the activated sludge process. Environ. Sci. Technol.2005.39:5816-5823.
[135]Ertl P, Simple quantum chemical parameters as an alternative to the Hammett Sigma Constants in QSAR Studies. Quant. Struct.-Act. Relat.1997.16:377-382.
[136]Bruno F, Curini R, Corcia A D, et al., Occurrence of sulfonamide antimicrobials in private water wells in Washington County, Idaho, USA. Chemosphere 2006.64:1963-1971.
[137]Diaz-Cruz S, Alda M L d, J. M, et al., Environmental behavior and analysis of veterinary and human drugs in soils, sediments and sludge. Trends in Analytical Chemistry 2003.6:340-351.
[138]Gu C, Karthikeyan K G, Sibley S D, et al., Complexation of the antibiotic tetracycline with humic acid. Chemosphere 2007.66:1494-1501.
[139]Benito-Pen E, Partal-Rodera A I, Leon-Gonzalez M E, et al., Evaluation of mixed mode solid phase extraction cartridges for the preconcentration of beta-lactam antibiotics in wastewater using liquid chromatography with UV-DAD detection. Analytica Chimica Acta 2006.556: 415-422.
[140]Riediker S, Rytz A, and Stadler R H, Cold-temperature stability of five P-lactam antibiotics in bovine milk and milk extracts prepared for liquid chromatography-electrospray ionization tandem mass spectrometry analysis. Journal of Chromatography A 2004.1054:359-363.
[141]Meyer M T, Bumgarner J E, Varns J L, et al., Use of radio immunoassay as a screen for antibiotics in confined animal feeding operations and confirmation by liquid chromatography/mass spectrometry. Sci. Total Environ.2000.248:181-187.
[142]Campagnolo E R, Johnson K R, Karpati A, et al., Antimicrobial residues in animal waste and water resources proximal to large-scale swine and poultry feeding operations. Sci. Total Environ. 2002.299:89-95.
[143]Stolker A A M and Brinkman U A T, Analytical strategies for residue analysis of veterinary drugs and growth-promoting agents in food-producing animals:a review. Journal of Chromatography A 2005.1067:15-53.
[144]Hirsch R, Ternes T, Haberer K, et al., Occurrence of antibiotic in the aquatic environment. Sci. Total Environ.1999.225:109-118.
[145]Xu W, G. Z, X. L, et al., Occurrence and elimination of antibiotics at four sewage treatment plants in the Pearl River Delta (PRD), South China. Water research 2007.41:4526-4534.
[146]Matsui Y, T. O, T. I, et al., Occurrence of a veterinary antibiotic in streams in a small catchment area with livestock farms. Desalination 2008.226:215-221.
[147]Karthikeyan K G and Meyer M T, Occurrence of antibiotics in wastewater treatment facilities in WI, USA.. Sci. Total Environ.2006.361:196-207.
[148]Halling-Sφrensen B, Nors Nielsen S, Lanzky P F, et al., Occurrence, fate and effects of pharmaceutical substances in the environment:a review. Chemosphere 1998.36:357-393.
[149]Langin A, Alexy R, konig A, et al., Deactivation and transformation products in biodegradability testing of (3-lactams amoxicillin and piperacillin. Chemosphere 2009.75: 347-354.
[150]Henninger A and Kummerer K, Promoting resistance by the emission of antibiotics from hospitals and households into effluent. Clin. Chim. Acta 2003.9:1203-1214.
[151]Xu W H, Zhang G, Zou S C, et al., Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry. Environ Pollut.2007.145: 672-679.
[152]Loganathan B, Phillips M, Mowery H, et al., Contamination profiles and mass loadings of macrolide antibiotics and illicit drugs from a small urban wastewater treatment plant. Chemosphere 2009.75:70-77.
[153]Terzic S, Senta I, Ahel M, et al., Occurrence and fate of emerging wastewater contaminants in Western Balkan Region. Sci. Total Environ.2008.399:66-77.
[154]Kostopoulou M and Nikolaou A, Analytical problems and the need for sample preparation in the determination of pharmaceuticals and their metabolites in aqueous environmental matrices. Trends in Analytical Chemistry 2008.27(11):1023-1035
[155]Koch D E, Bhandari A, Close L, et al., Azithromycin extraction from municipal wastewater and quantitation using liquid chromatography/mass spectrometry. Journal of Chromatography A 2005.1074:17-22.
[156]Gros M, Petrovic M, and Barcelo D, Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ero river basin (Northest Spain). Environ. Toxicol. Chem 2007.26:1553-1562.
[157]Gomez M J, Petrovic M, Fernandez-Alba A R, et al., Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography-tandem mass spectrometry analysis in hospital effluent wastewaters. Journal of Chromatography A 2006.1114: 224-233.
[158]Doll T E and Frimmel F H, Fate of pharmaceuticals-photodegradation by simulated sunlight. Chemosphere 2003.52:1757-1769.
[159]Vione D, Feitosa-Felizzola J, Minero C, et al., Phototransformation of selected human-used macrolides in surface water:Kinetics, model predictions and degradation pathways. Water research 2009.43:1959-1967.
[160]Kosjek T and Heath E, Applications of mass spectrometry to identifying pharmaceutical transformation products in water treatment. Trends in Analytical Chemistry 2008.27(10):807-820.
[161]Perez-Estrada L A, Agiiera A, Hernando M D, et al., Photodegradation of malachite green under natural sunlight irradiation:Kinetic and toxicity of the transformation products. Chemosphere 2008.70:2068-2075.
[162]Rao R N and Nagaraju V, An overview of the recent trends in development of HPLC methods for determination of impurities in drugs. Journal of Pharmaceutical and Biomedical Analysis 2003.33:335-377.
[163]Miguel L and Barbas C, LC determination of impurities in azithromycin tablets. Journal of Pharmaceutical and Biomedical Analysis 2003.33:211-217.
[164]Doll T E and Frimmel F H, Fate of pharmaceuticals-photodegradation by simulated solar UV-light. Chemosphere 2003.52:1757-1769.
[165]Jiao S, Zheng S, Yin D, et al., Aqueous oxytetracycline degradation and the toxicity change of degradation compounds in photoirradiation process. Journal of Environmental Sciences 2008. 20:806-813.
[2]Wang k, Livestock and Poultry Pollution Prevention Technology and Policy.6.2004:Chemical Industry Press.
[3]Tong L, Li P, Wang Y, et al., Analysis of veterinary antibiotic residues in swine wastewater and environmental water samples using optimized SPE-LC/MS/MS. Chemosphere 2009.74: 1090-1097.
[4]Ji M and Wu C, The harmful to the environment and the pre-release measures for intensive farming. Environmental Science & Technology 1999(2):32-32.
[5]Andara A R and Esteban J M L, Transition of particle size fractions in anaerobic digestion of the solid fraction of piggery manure. Biomass Bioenerg.2002.23:229-235.
[6]Sanchez E, Borja R, Travieso L, et al., Effect of organic loading rate on the stability, operational parameters and performance of a secondary upflow anaerobic sludge bed reactor treating piggery waste. Bioresour. Technol.2005.96:335-344.
[7]Torre A I D 1, Jimenez J A, Carballo M, et al., Ecotoxicological evaluation of pig slurry. Chemosphere 2000.41:1629-1635.
[8]Zhang H, Qu J, Liu H, et al., Isolation of dissolved organic matter in effluents from sewage treatment plant and evaluation of the influences on its DBPs formation. Separation and Purification Technology 2008.64:31-37.
[9]Levine A, Cripps S, and Lawler D. Benefits of particle size management for biological wastewater treatment.. in ASCE proceedings of the national conference on environmental engineering.1985. Boston, USA.
[10]Olboter L and Vogelpohl A, Influence of particle size distribution on the dewatering of organic sludges. Water Science and Technology 1993.28(1):149-157.
[11]Andara A and Esteban J M L, Transition of particle size fractions in anaerobic digestion of the solid fraction of piggery manure. Biomass & Bioenergy 2002.23:229-235.
[12]Seo D, Kim Y, Ham S, et al., Characterization of dissolved organic matter in leachate discharged from final disposal sites which contained municipal solid waste incineration residues. J. Hazard Mater.2007.148:679-692.
[13]Shon H, Vigneswaran S, Kim I S, et al., Fouling of ultrafiltration membrane by effluent organic matter:A detailed characterization using different organic fractions in wastewater. J. Membr. Sci.2006.278:232-238.
[14]Liu R X, Lead J R, and Baker A, Fluorescence characterization of cross flow ultrafiltration derived freshwater colloidal and dissolved organic matter. Chemosphere 2007.68:1304-1311.
[15]Her N, Amy G, Chung J W, et al., Characterizing dissolved organic matter and evaluating associated nanofiltration membrane fouling. Chemosphere 2008.70:495-502.
[16]Santos P, Otero M, Duarte R M B, et al, Spectroscopic characterization of dissolved organic matter isolated from rainwater. Chemosphere 2009.74:1053-1061.
[17]Leenheer J A, Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and wastewaters. Environmental Science & Technology 1981. 15:578-587.
[18]Imai A, Fukushima T, Matsushige K, et al., Characterization of dissolved organic matter in effluents from wastewater treatment plants. Water Research 2002.36:859-870.
[19]Jouraiphy A, Amir S, Winterton P, et al., Structural study of the fulvic fraction during composting of activated sludge-plant matter:Elemental analysis, FTIR and 13-C NMR. Bioresour. Technol.2008.99:1066-1072.
[20]Zhang T, Lu J F, Ma J, et al., Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation. Chemosphere 2008.71: 911-921.
[21]Ferrer I, Barber L B, and Thurman M, Gas chromatographic-mass spectrometric fragmentation study of phytoestrogens as their trimethylsilyl derivatives:identification in soy milk and wastewater samples. J. Chromatogr. A 2009.32:6024-6032.
[22]Lu F, Chang C H, Lee D J, et al., Dissolved organic matter with multi-peak fluorophores in landfill leachate. Chemosphere 2009.74:575-582.
[23]Baker A and Spencer R G M, Characterization of dissolved organic matter from source to sea using fluorescence and absorbance spectroscopy. Sci. Total Environ.2004.333:217-232.
[24]Chen J, LeBoef E J, Dai S, et al., Fluorescence spectroscopic studies of natural organic matter fractions. Chemosphere 2003.50:639-647.
[25]Park J-H, Spectroscopic characterization of dissolved organic matter and its interactions with metals in surface waters using size exclusion chromatography. Chemosphere 2009.4:485-494.
[26]Saadi I, Borisover M, Armon R, et al., Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements. Chemosphere 2006.63:530-539.
[27]Cai L, Koziel J A, Lo Y, et al., Characterization of volatile organic compounds and odorants associated with swine barn particulate matter using solid-phase microextraction and gas
chromatography-mass spectrometry-olfactometry. Journal of Chromatography A 2006.1102: 60-72.
[28]Schiffman S S, Bennett J L, and Raymer J H, Quantification of odors and odorants from swine operations in North Carolina. Agricultural and Forest Meteorology 2001.108:213-240.
[29]Thiebaut B, Lattuati-Derieux A, Hocevar M, et al., Application of headspace SPME-GC-MS in characterisation of odorous volatile organic compounds emitted from magnetic tape coatings based on poly (urethane-ester) after natural and artificial ageing. Polymer testing 2007.26: 243-256.
[30]Larreta J, Vallejo A, Bilbao U, et al., Experimental design to optimise the analysis of organic volatile compounds in cow slurry by headspace solid-phase microextraction-gas chromatography-mass spectrometry. Journal of Chromatography A 2006.1136:1-9.
[31]Zhu J, Areview of microbiology in swine manure odor control. Agriculture, Ecosystems and Environment 2000.78:93-106
[32]EPA, Phenols by Gas Chromatography:Capillary Column Technique, Environmental Protection Agency W, DC, Editor.1995. p.1.
[33]Dai C, Zeng K, Duan Y, et al., Treatment of fatty acid-containing wastewate. Industrial water & wastewater 2007.38(1):47-50.
[34]Brondz I, Development of fatty acid analysis by high-performance liquid chromatography, gas chromatography, and related techniques. Analytica Chimica Acta 2002.465:1-37.
[35]Pan L, Adams M, and Pawliszyn J, Determination of Fatty Acids Using Solid-Phase Microextraction. Analytical Chemistry 1995.67:4396-4403.
[36]Managaki S, Murate A, Takada H, et al., Distribution of macrolides, sulfonamides, and trimethoprim in tropical waters:ubiquitous occurrence of veterinary antibiotics in the Mekong Delta.. Environmental Science and Technology 2007.41:8004-8010.
[37]Alban L, Nielsen E, and Dahl J, A human health risk assessment for macrolide-resistant Campylobacter associated with the use of macrolides in Danish pig production. Prev. Vet. Med. 2008.83:115-129.
[38]FDA, New guidance for industry on antimicrobial drugs for food animals., Administration U Fa D, Editor.2003. p.35.
[39]Sarmah A K, Meyer M T, and Boxall A B A, A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment. Chemosphere 2006.65:725-759.
[40]Malintan N T and Mohd M A, Determination of sulfonamides in selected Malaysian swine wastewater by high-performance liquid chromatography. Journal of Chromatography A 2006.1127: 154-160.
[41]Nakata H, Kannan K, Jones P D, et al., Determination of Fluoroquinolone antibiotics in wastewater effluents by liquid chromatography mass spectrometry and fluorescence detection. Chemosphere 2005.58:759-766.
[42]Kemper N, Veterinary antibiotics in the aquatic and terrestrial environment. Ecological Indicators 2008.8:1-13.
[43]Hernandez F, Sancho J V, Ibanez M, et al., Antibiotic residue determination in environmental waters by LC-MS. Trends in Analytical Chemistry 2007.26(6):466-485.
[44]Diaz-Cruz M S, Garca-Galan M J, and Barcelo D, Highly sensitive simultaneous determination of sulfonamide antibiotics and one metabolite in environmental waters by liquid chromatography-quadrupole linear ion trap-mass spectrometry. Journal of Chromatography A 2008. 1193:50-59.
[45]Pierini E, Famiglini G, Mangani F, et al., Fate of Enrofloxacin in Swine Sewage. J. Agric. Food Chem.2004.52:3473-3477.
[46]Vieno N M, Tuhkanen T, and Kronberg L, Analysis of neutral and basic pharmaceuticals in sewage treatment plants and in recipient rivers using solid phase extraction and liquid chromatography-tandem mass spectrometry detection. Journal of Chromatography A 2006.1134: 101-111.
[47]Mcardell C S, Molnar E, Suter M J F, et al., Occurrence and fate of macrolide antibiotics in wastewater treatment plants and in the glatt valley watershed, Switzerland. Environmental Science & Technology 2003.37(24):5479-5486.
[48]Kummerer K, Antibiotics in the aquatic environment-A review. Chemosphere 2009.75(4): 417-441.
[49]Diaz-Cruz M S, Llorca M, and Barcelo D, Organic UV filters and their photodegradates, metabolites and disinfection by-products in the aquatic environment. Trends in Analytical Chemistry 2008.27(10):873-887.
[50]Deng L, Zheng P, Chen Z, et al., Improvement in post-treatment of digested swine wastewater. Bioresource Technology 2008.99:3136-3145.
[51]Weiland P, Anaerobic waste digestion in Germany-Status and recent developments. Biodegradation 2000(11):415-421.
[52]Ngoddy P O, Harper J P, and Gerrish J B, Enhanced treatment of livestock wastewater. J.agric.Engng. Res.1974.19:313-326.
[53]Glerum J C, Klomp G, and Poelma H R. The separation of solid and liquid parts of pig slurry. in In proceedings, international symposium on livestock wastes.1971. Ohio state university center.
[54]Lo K V, Liao P H, and Gao Y C, Anaerobic treatment of swine wastewater using hybrid UASB reactors. Bioresource Technology 1994.47:153-157.
[55]Deng L, Cai C, and Chen Z, The treatment of pig slurry by a full-scale anaerobic-adding raw wastewater-Intermittent aeration process. Biosystems Engineering 2007.98:327-334.
[56]Vanotti M B, Szogi A A, Hunt P G, et al., Development of environmentally superior treatment system to replace anaerobic swine lagoons in the USA. Bioresource Technology 2007.98: 3184-3194.
[57]Deng L, Zheng P, and Chen Z, Anaerobic digestion and post-treatment of swinewastewater using IC-SBR process with bypass of raw wastewate. Process Biochemistry 2006.41:965-969.
[58]Bortone G, Integrated anaerobic/aerobic biological treatment for intensive swine production. Bioresource Technology 2009.100(22):5424-5430.
[59]Edgerton B D, McNevin D, Wong C H, et al., Strategies for dealing with piggery effluent in Australia:the sequencing batch reactor as a solution. Water Science and Technology 1999.41(1): 123-126.
[60]Evans M R and Deans E A, The effect of temperature and residence time on aerobic treatment of pig slurry. Agricultural Wastes 1983(5):25-36.
[61]Zhu J, Areview of microbiology in swine manure odor control. Agr. Ecosystem Environ.2000. 78:93-106.
[62]Alaya S B, Haouech L, Cherif H, et al., Aeration management in an oxidation ditch. Desalination 2010.252(1-3):172-178.
[63]Hussain S, Aziz H A, Isa M H, et al., Physico-chemical method for ammonia removal from synthetic wastewater using limestone and GAC in batch and column studies. Bioresource Technology 2006.98:874-880.
[64]Hencha K R, Bissonnette G K, Sexstone A J, et al., Fate of physical, chemical, and microbial contaminants in domestic wastewater followingtreatment by small constructed wetlands. Water Research 2003.37:921-927.
[65]Wang Y F, Lin F, and Pang W Q, Ammonium exchange in aqueous solution using Chinese natural clinoptilolite and modifed zeolite. Journal of Hazardous Materials 2007.142:160-164.
[66]Rodgers M, Healy M G, and Mulqueen J, Organic carbon removal and nitrification of high strength wastewaters using stratified sand filters. Water Research 2005.39:3279-3286.
[67]APHA A P H A, Standard methods for the examination of water and wastewater,20th ed, APHA W, AWWA, Washington, D.C, USA, Editor.1998.
[68]Zhang H, Qu J, Liu H, et al., Characterization of isolated fractions of dissolved organic matter from sewage treatment plant and the related disinfection by-products formation potential. Journal of Hazardous Materials 2009.164:1433-1438.
[69]Obaja D, Mace S, and Mata-Alvarez J, Biological nutrient removal by a sequencing batch reactor (SBR) using an internal organic carbon source in digested piggery wastewater. Bioresour. Technol.2005.96:7-14.
[70]Bernet N, Delgenes N, Akunna J C, et al., Combined anaerobic-aerobic SBR for the treatment of piggery wastewater. Water Research 2000.34:611-619.
[71]Huo S, Xi B, Yu H, et al., Characteristics of dissolved organic matter (DOM) in leachate with different landfill ages. Journal of Environmental Sciences 2008.20:492-498.
[72]Her N, Amy G, McKnight D, et al., Characterization of DOM as a function of MW by fluorescence EEM and HPLC-SEC using UVA, DOC, and fluorescence detection. Water Research 2003.37:4295-4303.
[73]HAO R, CAO K, ZHAO G, et al., Ultraviolet Absorption Spectrum Characterization Approach for Quantitative Analysis of Dissolved Organic Contaminants in Sewag. Journal of Beijing University of Technology 2006.32(12):1062-1066.
[74]Ou Y, Lou Z, and Zhao Y, On relationship between COD values in leachate and their UV absorbance in various conditions. Journal of University of Science and Technology of Suzhou (Engineering and Technology) 2003.16(3):6-10.
[75]Lguirati A, Baddi G A, Mousadik A E, et al., Analysis of humic acids from aerated and non-aerated urban landfill composts. International Biodeterioration & Biodegradation 2005.56: 8-16.
[76]Rappert S and Muller R, Odor compounds in waste gas emissions from agricultural operations and food industries. Waste Manage.2005.25:887-907.
[77]Jensen M T, Cox R P, and Jensen B B,3-Methylindole (skatole) and indole production by mixed populations of pig fecal bacteria. Applied and Environment Microbiology 1995.61: 3180-3184.
[78]Boursier H, Beline F, and Paul. E, Piggery wastewater characterisation for biological nitrogen removal process design. Bioresource Technology 2005.96:351-358.
[79]Kaiser J P, Feng Y, and Bollag. J M, Microbial metabolism of pyridine, quinoline, acridine, and their derivatives under aerobic and anaerobic conditions. Microbiology Review 1996.60: 483-498.
[80]Zhang Z and Zhu J, Effectiveness of short-term aeration in treating swine finishing manure to reduce odor generation potential. Agriculture Ecosystems & Environment 2005.105:115-125.
[81]Lim T T, Heber A J, Ni J, et al., Odor and gas release from anaerobic treatment lagoons for swine manure. Journal of Environmental Quality 2003.32:406-416.
[82]Werker A G, Jennifer Becker, and Carly Huitema, Assessment of activated sludge microbial community analysis in full-scale biological wastewater treatment plants using patterns of fatty acid isopropyl esters (FAPEs). Water research 2003.37:2162-2172.
[83]Vedrenne F, Beline F, Dabert P, et al., The effect of incubation conditions on the laboratory measurement of the methane producing capacity of livestock wastes. Bioresource Technology 2008.99:146-155.
[84]Wong B, Show K, Su A, et al., Effect of volatile fatty acid composition on upflow anaerobic sludge blanket (UASB) performance. Energy Fuels 2008.22:108-112.
[85]Li Y, Gu G, Zhao J, et al., Anoxic degradation of nitrogenous heterocyclic compounds by acclimated activated sludge. Process Biochemistry 2001.37:81-86.
[86]Deslandes B, Gariepy C, and Houde A, Review of microbiological and biochemical effects of skatole on animal production. Livestock Production Science 2001.71:193-200.
[87]Zhu J, A review of microbiology in swine manure odor control. Agriculture Ecosystems & Environment 2001.78:93-106.
[88]Willig S, Lacorn M, and Claus R, Development of a rapid and accurate method for the determination of key compounds of pig odor. Journal of Chromatography A 2004.1038:11-18.
[89]Stashenko E E and Martinez J R, Derivatization and solid-phase microextraction. Trends in Analytical Chemistry 2004.23:553-561.
[90]Demeestere K, Dewulf J, Witte B, et al., Sample preparation for the analysis of volatile organic compounds in air and water matrices. Journal of Chromatography A 2007.1153:130-144.
[91]Romero J and Ventura F, Identification of 1,3-dioxanes and 1,3-dioxolanes as malodorous compounds at trace levels in river water, groundwater, and tap water.. Environmental Science & Technology 1998.32:206-216.
[92]Babol J, Squires E J, and Lundstrom K, Relationship between metabolism of androstenone and skatole in intact male pigs. Journal of Animal Science 1999.77:84-92.
[93]Zhou F, Li X, and Zeng Z, Determination of phenolic compounds in wastewater samples using a novel fiber by solid-phase microextraction coupled to gas chromatography. Analytica Chimica Acta 2005.538:63-70.
[94]Akesson-Nilsson G, Isolation of chlorinated fatty acid methyl esters derived from cell-culture medium and from fish lipids by using an aminopropyl solid-phase extraction column. Journal of Chromatography A 2003.996:173-180.
[95]Bagheri H and Saraji M, Conductive polymers as new media for solid-phase extraction: Isolation of chlorophenols from water sample. Journal of Chromatography A 2003.986:111-119.
[96]Polo M, Llompart M, Garcia-Jares C, et al., Development of a solid-phase microextraction method for the analysis of phenolic flame retardants in water samples. Journal of Chromatography A 2006.1124:11-21.
[97]Ballesteros-Gomez A, Rubio S, and Perez-Bendito D, Analytical methods for the determination of bisphenol A in food. Journal of Chromatography A 2009.1216:449-469.
[98]Loughrin J H, Comparison of solid-phase microextraction and stir bar sorptive extraction for the quantification of malodors in wastewater. Journal of Agricultural and Food Chemistry 2006.54: 3237-3241.
[99]Insa S, Besalu E, Iglesias C, et al., Ethanol/water extraction combined with solid-phase extraction and solid-phase microextraction concentration for the determination of chlorophenols in cork stoppers. Journal of Agricultural and Food Chemistry 2006.54:627-632.
[100]Olejniczak J and Staniewski J, Enrichment of phenols from water with in-situ derivatization by in-tube solid phase microextraction-solvent desorption prior to off-line gas chromatographic determination with large-volume injection. Journal of Analytica Chimica Acta 2007.588:64-72.
[101]Serrano E, Beltran J, and Hernandez F, Application of multiple headspace-solid-phase microextraction followed by gas chromatography-mass spectrometry to quantitative analysis of tomato aroma components. Journal of Chromatography A 2009.1216:127-133.
[102]Mardones C, Baer D, Silva J, et al., Determination of halophenolic wood preservant traces in milk using headspace solid-phase microextraction and gas chromatography-mass spectrometry. journal of Chromatography A 2008.1215:1-7.
[103]Stalikas C, Fiamegos Y, Sakkas V, et al., Developments on chemometric approaches to optimize and evaluate microextraction. Journal of Chromatography A 2009.1216:175-189.
[104]Nome R C and Carasek E, Comparative study of the use of flow through systems with and without air segmentation for determination of phenols by solid-phase microextraction-gas chromatography. Journal of Chromatography A 2004.59:387-391.
[105]Mejias R C, Mann R N, Moreno V G, et al., Optimisation of headspace solid-phase microextraction for the analysis of volatile phenols in wine. Journal of Chromatography A 2003. 995:11-20.
[106]Canosa P, Rodriguez I, Rubi E, et al., Optimization of solid-phase microextraction conditions for the determination of triclosan and possible related compounds in water samples. Journal of Chromatography A 2005.1072:107-115.
[107]Vinas P, Campillo N, Martinez-Castillo N, et al., Solid-phase microextraction on-fiber derivatization for the analysis of some polyphenols in wine and grapes using gas chromatography-mass spectrometry. journal of Chromatography A 2009.1216:1279-1284.
[108]Silva I, Rocha S M, and Coimbra M A, Headspace solid phase microextraction and gas chromatography-quadrupole ass spectrometry methodology for analysis of volatile compounds of marine alt as potential origin biomarkers. Analytica Chimica Acta 2009.635:167-174.
[109]Wait A D, Evolution of Organic Analytical Methods in Environmental Forensic Chemistry. Environmental Forensics 2000.1:37-46.
[110]Werker A G and Hall E R, Development and application of a fatty acid based microbial community structure similarity index. Environmetrics 2002.13:347-363.
[111]Werker A G, Applied microbial ecology for the control of wastewater treatment systems. Water 21, IWA 2001.13:38-42.
[112]Kornel Nagy, Annamaria Jakab, Jeno Fekete, et al., An HPLC-MS approach for analysis of very long chain fatty acids and other apolar compounds on octadecyl-silica phase using partly miscible solvents. Analytical Chemistry 2004.76:1935-1941.
[113]Thurnhofer S and Vetter W, A gas chromatography/electron ionization-mass spectrometry-selected ion monitoring method for determining the fatty acid pattern in food after formation of fatty acid methyl esters. Journal of Agricultural and Food Chemistry 2005.53: 8896-8903.
[114]Jalali-Heravi M and Vosough M, Characterization and determination of fatty acids in fish oil using gas chromatography-mass spectrometry coupled with chemometric resolution techniques. Journal of Chromatography A 2004.1024:165-176.
[115]Lin P, Marc A, and Janusz P, Determination of fatty acids using solid-phase microextraction. Analytical Chemistry 1995.67:4396-4403.
[116]Martin D, Antequera T, Gonzalez E, et al., Changes in the fatty acid profile of the subcutaneous fat of swine throughout fattening as affected by dietary conjugated linoleic acid and monounsaturated fatty acids. J. Agric. Food Chem 2007.55:10820-10826.
[117]Christian T, Schneider R J, Farber H A, et al., Determination of antibiotics residues in manure, soil, and surface waters. Acta Hydroch. Hydrobiol.2003.31:34-44.
[118]Giger W, Alder A C, Golet E M, et al., Occurrence and fate of antibiotics as trace contaminants in wastewaters sewage sludge and surface waters. Chimia 2003.57:485-491.
[119]Martinez-Carballo E, Gonzalez-Barreiro C, Scharf S, et al., Environmental monitoring study of selected veterinary antibiotics in animal manure and soils in Austria. Environ Pollut.2007.148: 570-579.
[120]Batt A L, Snow D D, and Aga D S, Occurrence of sulfonamide antimicrobials in private water wells in Washington County, Idaho, USA. Chemosphere 2006.64:1963-1971.
[121]Gros M, Petrovic M, and Damia B, Development of a multi-residue analytical methodology based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 2006.70:678-690.
[122]Managaki S, Murate A, Takada H, et al., Distribution of macrolides, sulfonamides, and trimethoprim in tropical waters:ubiquitous occurrence of veterinary antibiotics in the Mekong Delta. Environ. Sci. Technol.2007.41:8004-8010.
[123]Jemal M, Schuster A, and Whigan D B, Liquid chromatography/tandem mass spectrometry methods for quantification of mevalonic acid in human plasma and urine:method validation, demonstration of using a surrogate standard, and demonstration of unacceptable matrix e□ect in spite of use of a stable isotope analog internal standard. Rapid Commun. Mass Spectrom.2003.17: 1723-1734.
[124]Lindberg R, Jarnheimer P, Olsen B, et al., Determination of antibiotic substances in hospital sewage water using solid phase extraction and liquid chromatography/mass spectrometry and group analogue internal standards. Chemosphere 2004.57:1479-1488.
[125]Castiglioni S, Bagnati R, Fanelli R, et al., Removal of pharmaceuticals in sewage treatment plants in Italy. Environ. Sci. Technol.2006.40:357-363.
[126]Gomez M J, Petrovic M, Fernandez-Alba A R, et al., Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography-tandem mass spectrometry analysis in hospital effluent wastewaters. Journal of Chromatography A 2006.1114: 224-233.
[127]Lucchetti D, Fabrizi L, Esposito A, et al., Simple confirmatory method for the determination of erythromycin residues in trout:a fast liquid-liquid extraction followed by liquid chromatography-tandem mass spectrometry. J. Agric. Food Chem 2005.53:9689-9694.
[128]Kay P, Blackwell P A, and Boxall A B A, Column studies to investigate the fate of veterinary antibiotics in clay soils following slurry application to agricultural land. Chemosphere 2005.60: 497-507.
[129]Schubert J K, Miekisch W, Fuchs P, et al., Determination of antibiotic drug concentrations in circulating human blood by means of solid phase micro-extraction. Clin. Chim. Acta 2007.386: 57-62.
[130]Golet E M, Alder A C, Hartmann A, et al., Trace determination of fluoroquinolone antibacterial agents in urban wastewater by solid-phase extraction and liquid chromatography with fluorescence detection. Analytical Chemistry 2001.73:3632-3638.
[131]Vieno N, Tuhkanen T, and Kronberg L, Elimination of pharmaceuticals in sewage treatment plants in Finland, water research 2007.41:1001-1012.
[132]Connor S and Aga D S, Analysis of tetracycline antibiotics in soil:Advances in extraction, clean-up, and quantification. Trends in Analytical Chemistry 2007.26:456-465.
[133]Gros M, Petrovic M, and Damia B, Tracing Pharmaceutical Residues of Different Therapeutic Classes in Environmental Waters by Using Liquid Chromatography/Quadrupole-Linear Ion Trap Mass Spectrometry and Automated Library Searching. Analytical Chemistry 2009.81:898-912.
[134]Kim S, Eichhorn P, Jensen J N, et al., Removal of antibiotics in wastewater:effect of hydraulic and solid retention times on the fate of tetracycline in the activated sludge process. Environ. Sci. Technol.2005.39:5816-5823.
[135]Ertl P, Simple quantum chemical parameters as an alternative to the Hammett Sigma Constants in QSAR Studies. Quant. Struct.-Act. Relat.1997.16:377-382.
[136]Bruno F, Curini R, Corcia A D, et al., Occurrence of sulfonamide antimicrobials in private water wells in Washington County, Idaho, USA. Chemosphere 2006.64:1963-1971.
[137]Diaz-Cruz S, Alda M L d, J. M, et al., Environmental behavior and analysis of veterinary and human drugs in soils, sediments and sludge. Trends in Analytical Chemistry 2003.6:340-351.
[138]Gu C, Karthikeyan K G, Sibley S D, et al., Complexation of the antibiotic tetracycline with humic acid. Chemosphere 2007.66:1494-1501.
[139]Benito-Pen E, Partal-Rodera A I, Leon-Gonzalez M E, et al., Evaluation of mixed mode solid phase extraction cartridges for the preconcentration of beta-lactam antibiotics in wastewater using liquid chromatography with UV-DAD detection. Analytica Chimica Acta 2006.556: 415-422.
[140]Riediker S, Rytz A, and Stadler R H, Cold-temperature stability of five P-lactam antibiotics in bovine milk and milk extracts prepared for liquid chromatography-electrospray ionization tandem mass spectrometry analysis. Journal of Chromatography A 2004.1054:359-363.
[141]Meyer M T, Bumgarner J E, Varns J L, et al., Use of radio immunoassay as a screen for antibiotics in confined animal feeding operations and confirmation by liquid chromatography/mass spectrometry. Sci. Total Environ.2000.248:181-187.
[142]Campagnolo E R, Johnson K R, Karpati A, et al., Antimicrobial residues in animal waste and water resources proximal to large-scale swine and poultry feeding operations. Sci. Total Environ. 2002.299:89-95.
[143]Stolker A A M and Brinkman U A T, Analytical strategies for residue analysis of veterinary drugs and growth-promoting agents in food-producing animals:a review. Journal of Chromatography A 2005.1067:15-53.
[144]Hirsch R, Ternes T, Haberer K, et al., Occurrence of antibiotic in the aquatic environment. Sci. Total Environ.1999.225:109-118.
[145]Xu W, G. Z, X. L, et al., Occurrence and elimination of antibiotics at four sewage treatment plants in the Pearl River Delta (PRD), South China. Water research 2007.41:4526-4534.
[146]Matsui Y, T. O, T. I, et al., Occurrence of a veterinary antibiotic in streams in a small catchment area with livestock farms. Desalination 2008.226:215-221.
[147]Karthikeyan K G and Meyer M T, Occurrence of antibiotics in wastewater treatment facilities in WI, USA.. Sci. Total Environ.2006.361:196-207.
[148]Halling-Sφrensen B, Nors Nielsen S, Lanzky P F, et al., Occurrence, fate and effects of pharmaceutical substances in the environment:a review. Chemosphere 1998.36:357-393.
[149]Langin A, Alexy R, konig A, et al., Deactivation and transformation products in biodegradability testing of (3-lactams amoxicillin and piperacillin. Chemosphere 2009.75: 347-354.
[150]Henninger A and Kummerer K, Promoting resistance by the emission of antibiotics from hospitals and households into effluent. Clin. Chim. Acta 2003.9:1203-1214.
[151]Xu W H, Zhang G, Zou S C, et al., Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry. Environ Pollut.2007.145: 672-679.
[152]Loganathan B, Phillips M, Mowery H, et al., Contamination profiles and mass loadings of macrolide antibiotics and illicit drugs from a small urban wastewater treatment plant. Chemosphere 2009.75:70-77.
[153]Terzic S, Senta I, Ahel M, et al., Occurrence and fate of emerging wastewater contaminants in Western Balkan Region. Sci. Total Environ.2008.399:66-77.
[154]Kostopoulou M and Nikolaou A, Analytical problems and the need for sample preparation in the determination of pharmaceuticals and their metabolites in aqueous environmental matrices. Trends in Analytical Chemistry 2008.27(11):1023-1035
[155]Koch D E, Bhandari A, Close L, et al., Azithromycin extraction from municipal wastewater and quantitation using liquid chromatography/mass spectrometry. Journal of Chromatography A 2005.1074:17-22.
[156]Gros M, Petrovic M, and Barcelo D, Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ero river basin (Northest Spain). Environ. Toxicol. Chem 2007.26:1553-1562.
[157]Gomez M J, Petrovic M, Fernandez-Alba A R, et al., Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography-tandem mass spectrometry analysis in hospital effluent wastewaters. Journal of Chromatography A 2006.1114: 224-233.
[158]Doll T E and Frimmel F H, Fate of pharmaceuticals-photodegradation by simulated sunlight. Chemosphere 2003.52:1757-1769.
[159]Vione D, Feitosa-Felizzola J, Minero C, et al., Phototransformation of selected human-used macrolides in surface water:Kinetics, model predictions and degradation pathways. Water research 2009.43:1959-1967.
[160]Kosjek T and Heath E, Applications of mass spectrometry to identifying pharmaceutical transformation products in water treatment. Trends in Analytical Chemistry 2008.27(10):807-820.
[161]Perez-Estrada L A, Agiiera A, Hernando M D, et al., Photodegradation of malachite green under natural sunlight irradiation:Kinetic and toxicity of the transformation products. Chemosphere 2008.70:2068-2075.
[162]Rao R N and Nagaraju V, An overview of the recent trends in development of HPLC methods for determination of impurities in drugs. Journal of Pharmaceutical and Biomedical Analysis 2003.33:335-377.
[163]Miguel L and Barbas C, LC determination of impurities in azithromycin tablets. Journal of Pharmaceutical and Biomedical Analysis 2003.33:211-217.
[164]Doll T E and Frimmel F H, Fate of pharmaceuticals-photodegradation by simulated solar UV-light. Chemosphere 2003.52:1757-1769.
[165]Jiao S, Zheng S, Yin D, et al., Aqueous oxytetracycline degradation and the toxicity change of degradation compounds in photoirradiation process. Journal of Environmental Sciences 2008. 20:806-813.
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