類別:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/200
2024-03-06T02:47:28Z高級氧化處理程序對於游泳池中消毒副產物生成之影響
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/68746
標題: 高級氧化處理程序對於游泳池中消毒副產物生成之影響; Impacts of Advanced Oxidation Processes (AOPs) on Disinfection By-products Formation from Swimming Pools Water
作者: Wei-Kai Fang; 方暐凱
摘要: 游泳池普遍會透過加氯消毒程序以維持水質安全並避免水媒疾病的傳播。不過在加氯消毒的過程當中,游泳池中的天然有機物以及泳客在游泳過程中所產生的有機物 (例如汗液及尿液) 會與氯進行反應,進而產生對人體健康造成危害的消毒副產物,包括三鹵甲烷 (Trihalomethanes, THMs)、含鹵乙酸 (Haloacetic acids, HAAs)以及含鹵乙腈 (Haloacetonitriles, HANs) 等。然而游泳池基於維護以及管理成本的考量,大多會使用水循環系統且鮮少更換池水,也因此增加有機前質與氯的反應機會及時間,進而導致游泳池水中消毒副產物的持續生成並且不斷地累積在泳池當中,也使得泳客有較高的消毒副產物暴露量。因此,為了減少游泳池水中的消毒副產物,除了透過定期換水之外,也能利用高級氧化處理程序 (例如UV/chlorine及UV/H2O2) 當中所生成的自由基,利用其高氧化力將有機前質降解成中間副產物甚至是無機物。以UV/H2O2為例,過程中所產生的氫氧自由基,能夠有效地將大分子有機物降解成小分子,同時也能夠有效地減少消毒副產物的生成潛能。
本研究首先針對游泳池進行環境採樣,監測並了解水質變化以及消毒副產物濃度。採樣地點為國立台灣大學綜合體育館溫水游泳池,採樣時間分別為2016年八月、十月以及2017年二月。其後對於不同高級氧化處理條件進行批次模擬實驗,比較不同紫外光強度以及氧化處理程序對於水中非氣提性溶解性有機碳 (non-purgeable dissolved organic carbon, NPDOC)的降解趨勢、消毒副產物的減少及其有機前質的降解效率之影響。
環境採樣結果顯示此游泳池的水質特性、NPDOC以及消毒副產物濃度趨勢變化並不明顯。由於游泳池是使用先臭氧後加氯的消毒程序,因此消毒副產物濃度略不同於加氯消毒的泳池,尤其是以含鹵乙酸的減少較為明顯,此情形也與過去文獻的觀察相符。
關於高級氧化處理條件改變的影響,首先紫外光強度對於高級氧化處理效率有很顯著的影響,不論是NPDOC的減少、消毒副產物以及其前質的變化和降解都隨著紫外光劑量上升以及氫氧自由基生成量增加而有所提升。然而當紫外光強度不足時,即使給予足夠的氧化時間對於氧化初期所增加的含鹵乙酸前質仍然無法有效地降解。
至於不同氧化處理方法的影響,結果顯示單獨使用UV以及UV/chlorine處理對於有機物的礦化作用影響較不顯著;反觀UV/H2O2氧化過程中,隨著氫氧自由基的增加,有機碳濃度也隨之下降。消毒副產物的部分,在三種不同處理方法之下三鹵甲烷均較含鹵乙酸難以降解,因其含有立體結構所以不易被光解。此外,氫氧自由基對於具有立體結構之化合物有較小的反應速率常數,因此需要較長的反應時間才能有效地降解。在UV/chlorine反應過程當中,消毒副產物濃度隨反應快速地增加,包括三鹵甲烷、含鹵乙腈等,即便反應一段時間後能夠減少其含量,但相較於未反應前之濃度仍有明顯地增加。另外,單獨UV處理會增加含溴之三鹵甲烷之生成比例,此現象可歸因於含溴大分子有機物經由光解後,會促使溴離子的生成,並於後續加氯過程中形成次溴酸,促使含溴消毒副產物生成。
有機前質經過三種不同處理方法之後,其變化趨勢均略有不同。單獨UV處理之後會使黃酸類物質增加,而此與三鹵甲烷之生成潛能上升之結果相符。有機物經過UV/chlorine處理過後,可以看到明顯的減少趨勢,推測可能與有機物於處理過程中與氯進行反應產生消毒副產物有關;而經過UV/H2O2處理後可觀察到芳香族蛋白質類的化合物於反應初期產生,此情形也與消毒副產物的生成潛能於反應初期上升有關。; Chlorine-based disinfectants are widely used in swimming pools to maintain water quality and inhibit the spreads of waterborne diseases. During chlorination, natural organic matter (NOM) and swimmers-derived organic matter (such as perspiration and urine) will react with chlorine to generate disinfection by-products (DBPs) such as trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs) and which are harmful to human health. However, owing to the cost of maintenance and management, most of swimming pools use recirculation system and seldom replace the whole pool water with fresh water, result in the accumulation of DBPs in water thus swimmers will have higher exposure of DBPs. In addition to replace pools water frequently, DBPs can also be minimized by the free radicals generated from advanced oxidation processes (AOPs), including UV/chlorine and UV/H2O2. The high oxidation power of free radicals can degrade organic precursors into intermediate by-products or inorganic matters. Taking UV/H2O2 for example, the formation of hydroxyl radials can efficiently degrade higher molecular weight organic matters into smaller species and reduce the DBPs formation potentials (DBPFPs).
The first part of this study was field sampling for monitoring of water quality and the occurrences of DBPs. The sampling location was National Taiwan University (NTU) Sports Center indoor swimming pool and the samples were taken in August, October of 2016 and February of 2017. Secondly, bench scale simulations were conducted with different operation conditions of AOPs to compare their effects on non-purgeable dissolved organic carbon (NPDOC) degradation, DBPs formation and DBPs precursors’ reductions.
The results of field sampling showed that the variations of water quality including NPDOC and DBPs were not apparent. Owing to the type of disinfectant in the swimming pool was ozone combined with chlorine, the concentrations of DBPs were slightly differ from those observed in chlorinated swimming pools; especially the HAAs reduction which was consistent with previous studies. As for the change of operation conditions during AOPs, the results showed that increases of UV intensities had significant effects on NPDOC reduction, DBPs and their precursors’ alterations and degradation; and the efficiencies increased with the increasing UV intensities. However, when the UV intensities were insufficient, the HAAs precursors were be increased and a longer oxidation time could not efficiently degrade the HAAs precursors. As for the effects on organic matter among various oxidation processes, single UV and UV/chlorine treatments had slightly effects on organic matter mineralization; however, the NPDOC concentrations decreased gradually with the generation of hydroxyl radicals during the UV/H¬2O2 processes. The degradation efficiencies of HAAs were better than those of THMs among different oxidation treatments because THMs had steric hindrance itself therefore they were hard to be oxidized by free radicals or UV irradiation. In the reaction of UV/chlorine, concentrations of THMs, HANs and other DBPs would increase rapidly. Although DBPs concentrations decreased after a longer oxidation time with UV/chlorine treatments, they were still higher than the initial DBPs concentrations. Additionally, the reactions of single UV would increase the portion of Br-THMs which could be attributed to the release of bromide ion from large molecular compound and promoted the formation of hypobromous acid (HOBr).
The tendencies of organic precursors among various oxidation processes were different. Through the UV treatments, the fulvic acid-like organic matters would increase and which were coincided with the elevated THMFPs. In the UV/chlorine treatments, it could be observed that organic matters had apparent degradation which could be associated with organic matters reacted with chlorine for the formation of DBPs; while during UV/H2O2 treatments, the portion of aromatic protein compounds increased initially, thus this was slightly consistent with the increasing DBPFPs.2017-01-01T00:00:00Z高級氧化前處理對消毒副產物生成之影響
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/36004
標題: 高級氧化前處理對消毒副產物生成之影響; Effects of AOP Pre-treatment on DBPs Formations
作者: Pei-Lin Huang; 黃珮琳
摘要: 飲用水加氯消毒是台灣普遍採行之處理程序,然而氯會與水中有機物形成含氯消毒副產物,當水體有溴離子時則生成含溴消毒副產物,前者的致癌性與後者的生殖危害同樣值得重視。文獻指出pH 值、氯溴比及前質組成均影響消毒副產物之生成,然而文獻多關心單一參數或中性環境下之變化,缺乏整合各參數間之交互作用。本研究欲探討水中影響含氯、含溴消毒副產物生成之因素,並觀察以UV/H2O2前處理含溴水體後,消毒副產物生成潛能及物種分佈之變化。
前質試驗中選擇芳香族、脂肪族前質,添加不同濃度溴離子以改變氯溴比,分別觀察pH 7及pH 9之DBPFP濃度及物種分佈。發現任何條件下,芳香族前質僅生成含氯消毒副產物,可能因空間阻礙(steric hindrance)阻擋大分子HOBr與前質反應;脂肪族前質不具上述阻礙,易與反應速率較快之HOBr形成含溴消毒副產物。此外,芳香族前質偏好pH 7之環境,脂肪族前質則於pH 9較活躍。
本研究選擇金門太湖原水及實驗室配製前質作為實驗水樣,以UV及UV/H2O2前處理進行60∼120分鐘之氧化程序。UV反應過程中NPDOC無明顯變化,紫外光直接降解雙鍵導致DBPFP些微減少;UV/H2O2程序可有效降解NPDOC,然而DBPFP皆呈現先升後降之趨勢,在反應10分鐘達到最高點後才逐漸下降。可能由於氫氧自由基與有機物鍵結形成醇、酮類,增加水中消毒副產物之前質。
UV/H2O2程序不改變水中溴離子濃度,也不生成致癌性的溴酸鹽。若能確保高壓紫外燈之催化效率,有效縮短反應時間,UV/H2O2程序具應用於含溴金門原水之潛力。; Chlorination disinfection is a common water treatment process in Taiwan, generating toxic chlorinated disinfection by-products (DBPs). Unfortunately, Br-DBPs are also formed in presence of bromide. Cl-DBPs and Br-DBPs have received much public concern about their different health effects on carcinogenicity and reproduction damages. Therefore, the objective of this study is to evaluate bromide concentration, pH and precursor structures in drinking water to determine their influences on formation and distribution of THM and HAA. And this study also concerned about the changes of influencing factors and DBPFP in UV/H2O2 oxidation.
Aromatic and aliphatic precursors and different bromide concentration were evaluated for the distribution of Cl-DBP and Br-DBP under chlorination at pH 7 and pH 9. Steric hindrance limited the aromatic precursors to Cl-DBPs under whole conditions. The aliphatic precursors tended to form Br-DBPs. Besides, the aromatic precursors were more reactive at pH 7, and the aliphatic one at pH 9.
Tai lake water (Kinmen, Taiwan) and humic acids were selected in this study. In the UV/H2O2 process, THMFP or HAAFP increased within 10 min of irradiation and began to decrease after 30 min. OH-radicals seemed to increase DBPFP because which was not observed using UV irradiation without hydrogen peroxide. The bromide concentration remained stable and no bromate was formed under all irradiation time. The optimum effectiveness of UV/H2O2 process should be reached in application of bromide-rich Kinmen water.2005-01-01T00:00:00Z高溫暴露評估技術及高溫與噪音共同暴露健康效應研究
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/28090
標題: 高溫暴露評估技術及高溫與噪音共同暴露健康效應研究; Study on exposure assessment of heat stress and the combined effects of heat stress and noise exposure
作者: Yow-Jer Juang; 莊侑哲
摘要: 熱壓力在大多數位於熱帶及亞熱帶地區的國家及其工作環境已是一個普遍存在具有季節性的職業與環境衛生問題,尤其是像台灣這種既熱且濕的地理環境,要如何避免因熱壓力引起的相關疾病,一直是環境衛生實務工作者必須面對的問題。本論文的研究目的主要是利用自行設計以冷凍庫板所建造之熱暴露艙,在進行穩定性與均勻性評估後,探討高溫暴露評估技術,並配合搭設放音系統進行高溫與噪音共同暴露之健康效應之研究。
高溫暴露評估技術的研究部分,首先在不同環境參數組合的81種實驗條件下,評估其對自然濕球溫度及標準黑球溫度測值的影響,其次則是同時測定131組實驗條件之氣溫、相對濕度、黑球溫度、風速與自然濕球溫度,利用Statistica 6.0統計軟體進行複回歸分析,建立自然濕球溫度之預測模式,並配合利用既有的氣象因素加上黑球溫度測值求得綜合溫度熱指數之預測值供民眾參考以預防熱危害之可行性。
高溫與噪音共同暴露之健康效應之研究部分,則利用熱暴露艙架設放音系統模擬高溫與噪音同時暴露之環境,徵求志願受測者至公立醫院實施健康檢查後進行本實驗,本研究係採用田口實驗設計法將綜合溫度熱指數、噪音音壓級、暴露時間與工作負荷量四項變數利用L9 的直交表進行高溫與噪音共同暴露的暫時性聽力損失之探討。
高溫暴露評估技術的研究結果發現,當有輻射熱源存在時,黑球的尺寸與輻射溫度愈大其黑球溫度測值也愈大,並且隨著黑球尺寸的加大,其回應時間也愈長;而風速愈大則將使其測值變小,如僅有相對濕度改變時則對黑球溫度測值無影響。在風速小於2.60 m/s之所有測試條件下,自然濕球溫度均較通風濕球溫度測值大;而且自然濕球溫度測值隨氣溫、相對濕度與輻射溫度增加而增加,但隨風速增加而降低。當熱環境的氣溫大於皮膚溫度並伴隨有明顯的輻射熱源存在時,則風速愈大會造成自然濕球溫度、黑球溫度測值與綜合溫度熱指數愈低而導致熱壓力評估的判斷錯誤。同時針對開發自然濕球溫度預測模式部份,經複迴歸分析後,發現自然濕球溫度與環境參數具有高度之相關性,其複迴歸方程式為Tnwb = 0.81×Ta + 0.05×Tg + 0.15×RH - 0.35×Va - 9.98 (R=0.996)。經初步驗證,本研究所開發之自然濕球溫度預測模式其預測值與實測值的誤差均小於1 ℃。又利用熱暴露艙探討高溫與噪音共同暴露效應的研究發現,暫時性聽力損失程度主要是取決於噪音暴露劑量並會受到工作負荷與高溫同時暴露而導致聽力損失的增加,並且暫時性聽力損失的恢復時間則由噪音暴露後的損失程度所決定。
綜合上述,利用本研究所開發之綜合溫度熱指數之預測模式,提出以綜合溫度熱指數當作高溫氣象預報指標供大眾媒體預防熱相關疾病之參考,並建議國內因應全球氣候暖化的問題,應積極進行高溫與其他環境的化學因素或是物理因素共同暴露效應的相關研究。; The heat stress is one of major occupational and environmental health issues for workers and residents in the tropical and subtropical areas. The prevention of heat-related illness caused by heat stress is always the important topic for occupational hygiene practitioners, especially in Taiwan with hot and humid climate. The aims of this study are to develop the assessment techniques for thermal exposure of and health effects with simultaneous exposure to heat and noise. A climate chamber made of steel plate packed with polyurethane foam was optimized and used for the experiment.
For the thermal exposure assessment technique, we first developed 81 experimental conditions of different environmental parameters to evaluate effects of natural wet bulb temperature and globe temperature. Second, 131 sets of experimental data including air temperatures, relative humidities, globe temperatures, air velocities and natural wet bulb temperatures were generated with the prediction model of natural wet bulb temperature and analyzed using multiple regression analysis. Designed thermal and noise exposure conditions were simulated in the chamber to study the combined effects among volunteers who had received medical examination before the experiment. The L9 orthogonal array of different levels of wet bulb globe temperature, noise intensity, exposure duration and workload was determined by adopting Taguchi’s method.
It was found that globe temperature increases with the size of globe and radiant temperature when radiant heat appears, but decreases with the increasing air velocity. However, the change of relative humidity has no effect on the measurement of globe temperature. In addition, the increasing response time of globe temperature is observed for greater globe size. For air velocity smaller than 2.60 m/s, natural wet bulb temperature was found to be greater than psychrometric temperature. And measurement of natural wet bulb temperature will increase with air temperature, relative humidity and radiant temperature, but the trend is reversed when air velocity increases. Therefore, greater air velocity will result in smaller natural wet bulb temperature, globe temperature and wet bulb globe temperature, which leads to the misjudgment on heat stress. According to multiple regression analysis, it was found that natural wet bulb temperature is highly correlated with the environmental parameters. The prediction model is expressed as Tnwb = 0.81×Ta + 0.05×Tg + 0.15×RH - 0.35×Va - 9.98 (R=0.996), and the error is within 1 ℃. From the investigation of combined effects of heat and noise and workload exposure, it was observed that the temporary threshold shift driven by noise exposure is enhanced by heat and workload. The recovery time of temporary threshold shift is determined by the degree of hearing loss after noise exposure.
In conclusion, this study proposed wet bulb globe temperature obtained by prediction model as a heat stress index for the prevention of heat-related illness. Further research on health effect induced by combined exposure of chemical and physical agents are suggested to meet the problem of global warming.2007-01-01T00:00:00Z養豬廢水中四環黴素與磺胺類藥物之測定
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/64214
標題: 養豬廢水中四環黴素與磺胺類藥物之測定; Determination of Tetracyclines and Sulphonamides in Swine Wastewater
作者: Jia-Mei Lin; 林嘉美
摘要: 畜牧業為了能夠快速且大量提供產品以因應市場需求而逐漸發展成為集中型飼育場,其特點為單一種類地飼養牲畜且圈地狹小。狹窄而集中的飼養場地使牲畜較容易患病進而引發大規模的感染,因此使用抗生素作為疾病的治療與預防在畜牧業中相當重要。此外,低於治療劑量的抗生素使用也被發現具有促進牲畜生長的效果,因此抗生素也曾被添加在飼料中投藥給牲畜作為生長促進劑。四環黴素與磺胺類藥物均為曾被廣泛使用的畜牧業用藥,且可能隨著畜牧業廢水排放至環境水體中,造成環境微生物中抗藥性基因的篩選。
本研究為偵測畜牧業廢水中進流水與放流水,以及河水中的四環黴素與磺胺類藥物之方法開發。分析物為三種四環黴素:氯四環黴素(chlortetracycline)、羥四環黴素(oxytetracycline)與四環黴素(tetracycline)以及八種磺胺類藥物:磺胺嘧啶(sulfadiazine)、磺胺塞唑(sulfathiazole)、磺胺甲嘧啶(sulfamerazine)、磺胺二甲嘧啶(sulfamethazine)、磺胺間甲氧嘧啶(sulfamonomethoxine)、磺胺甲噁唑(sulfamethoxazole)、磺胺二甲氧基嘧啶(sulfadimethoxine)與磺胺喹噁啉(sulfaquinoxaline)。
採得之水樣以甲酸調整pH值至pH 3,並保存於4℃中。本方法取10毫升進流水、20毫升放流水與100毫升河水進行樣本前處理。各水樣添加同位素標定的四環黴素與磺胺類藥物作為內對照標準品,並以2 mg/mL比例添加EDTA (ethylenediaminetetraacetic acid)以防止四環黴素與二價金屬離子螯合。水樣於3,000 rpm (1411 xg)離心20分鐘以去除泥沙。水樣上清液通過HLB固相萃取管柱(事先以2毫升甲醇與2毫升Milli-Q純水通過萃取管柱)進行萃取,再以1.6毫升甲醇進行沖提。沖提液以0.22 μm PVDF濾膜過濾後減壓離心濃縮至近乾,再以200微升20%甲醇與水溶液回溶,進樣15微升以極致液相層析/串聯式質譜儀使用電灑游離正離子模式(ESI+)與選擇性反應偵測模式(SRM)分析待測物。
基質效應評估中可見進流水中各待測物訊號僅剩10%-30%,放流水中則為40%-80%,河水中則為85%-100%,顯示進流水中的待測物受到強烈的訊號抑制。本研究將進流水樣本萃取液進一步稀釋2.5倍與5倍,結果發現稀釋確實可降低基質效應的訊號抑制,但待測物的訊號也因稀釋而降低,反而不利於偵測。萃取效率評估中可見進流水中各待測物訊號僅剩40%-70%,放流水中則為100%-120%,河水中則為50%-85%,顯示進流水中待測物可能吸附於水樣中的懸浮微粒使得萃取效率較低。本研究透過進一步實驗,分為同位素內標準品前添加於樣本,與同位素內標準品添加於樣本離心後上清液兩組,發現進流水的待測物訊號在前添加樣本和上清液添加樣本的差異明顯大於放流水與河水,顯示進流水中所含有的較多的懸浮微粒確實會因吸附作用而影響到待測物的萃取效率。進流水中各待測物的回收率為70%-130%,放流水中為65%-140%,河水則為70%-120%。由於三種水樣各待測物的回收率大多介於70%-130%,顯示使用同位素內標的同位素稀釋技術可準確地定量複雜樣本中的待測物。無論日內差與日間差之分析,測定濃度與添加濃度相比的定量誤差在多數待測物中均小於30%,而重複樣本的相對標準偏差(RSD%)在多數待測物中亦小於30%。
四環黴素與磺胺類藥物在進流水中的定量極限分別為2.3 μg/L-2.9 μg/L與1.0 μg/L-2.7 μg/L,在放流水中的定量極限分別為266 ng/L-367 ng/L與93.5 ng/L-351 ng/L,在河水中的定量極限則分別為20.4 ng/L-53.8 ng/L與14.7 ng/L-36.9 ng/L。
本研究分析實際養豬場所採集之進流水與放流水,三種四環黴素在各養豬場進流水中均可被偵測到,濃度範圍大多約為每公升水樣中有數十至數百微克四環黴素。經過廢水處理後,三種四環黴素的濃度降至每公升水樣中有數微克。大多數的磺胺類藥物在進流水與放流水中低於偵測極限,除了sulfamethazine在一座養豬場的進流水和放流水樣本中較高(約600 μg/L)。在鄰近養豬場的河水樣本中,大多數的待測物均低於偵測極限,除了chlortetracycline (160 ng/L-1,070 ng/L)與sulfamethazine (36.8 ng/L)。本研究也分析淡水河流域中各採樣點的河水,發現絕大多數待測物均低於偵測極限,除了sulfamethoxazole在第11號採樣點中測得26.4 ng/L。
本研究開發了在畜牧業廢水與河水中偵測四環黴素與磺胺類藥物的方法,未來可應用於更多實際環境樣本的分析,以確認廢水中待測物的濃度。本研究除了環境監控之外,也可為環境微生物中抗藥性基因篩選的研究提供環境水體中藥物濃度偵測的方法。; The animal husbandry industry demands a large amount of veterinary antibiotics in concentrated animal feeding operations (CAFOs) on treating and preventing from diseases as well as on promoting growth. To evaluate the potential impact of antibiotics releasing into the environment, a good analytical method is essential for measuring veterinary antibiotics in environmental matrixes.
Tetracyclines and sulphonamides are broad-spectrum antibacterial agents, and were once heavily used in animal husbandry and as feed additives. This study developed a method to determine three tetracyclines, including chlortetracycline, oxytetracycline, as well as tetracycline, and eight sulphonamides, including sulfadiazine, sulfathiazole, sulfamerazine, sulfamethazine, sulfamonomethoxine, sulfamethoxazole, sulfadimethoxine in swine wastewater and river water using deuterium-labeled tetracycline (tetracycline-deuterium 6) and sulphonamides (sulfamerazine-deuterium 4, sulfamethoxazole-deuterium 4, sulfadimethoxine-deuterium 4) as internal standards.
All water samples were adjusted to pH 3 by formic acid, and then were stored at 4℃. Ten millimeters of influent, 20 mL of effluent, and 100-mL river water were used and isotope-labeled standards were added at the beginning of sample preparation. EDTA was also added (2 mg/mL) to prevent the tetracyclines from chelating with divalent metal ions. The samples were centrifuged under 3,000 rpm (1,411 xg) for 20 minutes, then the supernatants underwent solid-phase extraction (SPE) with hydrophilic-hydrophobic balance (HLB) cartridges, which were conditioned with 2 mL methanol and 2 mL Milli-Q water before extractions. Analytes were eluted with 1.6 mL of methanol, filtered with 0.22-μm PVDF filters, and were concentrated to barely dry by a SpeedVac concentrator. The residues were reconstituted with 200 μL of 20% methanol/80% water, and 15 μL were injected onto the ultra-high performance liquid chromatography/tandem mass spectrometry at positive electrospray ionization and with selected reaction monitoring.
Matrix effect factors of analytes in influent, effluent and river water were 10%-30%, 40%-80%, and 85%-100%, respectively, indicating serious ion suppression in influent. This study diluted post-spiked influent samples with 2.5 and 5 times, respectively, and found that the dilutions decreased not only matrix suppression effect but also the signal intensities of analytes; thus, the eluent was not further diluted before the instrumental analysis. The extraction efficiencies of analytes in influent, effluent and river water were 40%-70%, 100%-120%, and 50%-85%, respectively. The signal intensity of internal standards in pre-spiked samples of influent, effluent, and river water were 45%-65%, 83%-90%, and 88%-120%, respectively, comparing with those in spiked supernatant samples, these indicated that analytes may adsorb to the particles in influent and may be removed at the step of centrifugation. The recoveries of analytes in influent, effluent and river water were 70%-130%, 65%-140%, and 70%-120%, respectively; recoveries of most analytes were 70%-130%, demonstrating that isotope-labeled internal standards could compensate the influence on quantitation from the matrix effect and analytes adsorption to the particles. Most inter-day and intra-day quantitative biases (accuracy) were below 30%, and inter-day and intra-day RSD% precision were also below 30% on most analytes.
The limits of quantitation of tetracyclines and sulphonamides were 2.3 μg/L-2.9 μg/L and 1.0 μg/L-2.7 μg/L in influent, 266 ng/L-367 ng/L and 93.5 ng/L-351 ng/L in effluent, and 20.4 ng/L-53.8 ng/L and 14.7 ng/L-36.9 ng/L in river water, respectively.
The concentrations of tetracyclines in influent and effluent of piggery farms were detected at tens to hundreds of micrograms per liter in influent and were below 10 μg/L in effluent. Most sulphonamides in influent and effluent of piggery farms were below detection limits, except for sulfamethazine from one site (around 600 μg/L in the influent and effluent). The concentrations of most tetracyclines and sulphonamides in river water nearby a piggery farm were below detection limits, except for chlortetracycline (160 ng/L-1,070 ng/L) and sulfamethazine (36.8 ng/L) in one sample. Most analytes were below detection limits in Dan-Shui River, except for sulfamethoxazole (26.4 ng/L) in one sample.
This study provides an accurate and precise method for determining tetracyclines and sulphonamides in swine wastewater and river water. The method is useful for researches in environment fate and monitoring of tetracyclines and sulphonamides. More analyses on field samples are desired for clarifying the background concentrations of tetracyclines and sulphonamides in swine wastewater and river, and their potential impact on the environment.2012-01-01T00:00:00Z