||Evaluation of anthropogenic impacts on reservoir water quality by monitoring the occurrence of emerging contaminants
||Department of Environmental Engineering
近年來，飲用水安全問題受到社會大眾的矚目，而台灣地狹人稠，水源保護區常與經濟活動區域相鄰，使得水源面臨遭受人類活動汙染的風險，因此了解水源區內不同程度、不同類別的人類行為對於水質的影響相形重要，政府得以對於重點汙染區域進行汙染控制。故本研究針對一集水區土地利用複雜、人為活動密集之阿公店水庫，進行為期一年的水中新興汙染物與一般水質參數監測，監測項目包括四個農藥為嘉磷塞(glyphosate)、固殺草(glufosinate)、甲基多保淨(thiophanate-methyl)、芬殺松(fenthion)，及兩個農藥代謝物aminomethylphosphonic acid和fenthion sulfoxide，一抗生素為氧四環素(oxytetracycline)，一內分泌干擾物質為雙酚A(bisphenol A)，共八個新興汙染物，並以農藥對應農業活動，抗生素反映畜牧、養殖活動，內分泌干擾物質代表一般人口居住，採樣從2017年3月開始至2018年2月，每月1次，總共11個月。
119個樣品結果顯示，這些汙染物在水中的濃度首先反映出本身的物理化學性質，水溶性高、較為親水的物質有較高的檢出濃度及檢出頻率，分別為氧四環素1.82±2.28 μg/L, 59.7%、嘉磷塞0.23±0.57 μg/L, 32.8%、及其代謝物aminomethylphosphonic acid 0.25±0.55 μg/L, 38.0%、固殺草0.20±0.85 μg/L, 16.8%；而水溶性低的雙酚A濃度雖不高(0.035±0.076 μg/L)，檢出頻率高達33.6%，與嘉磷塞檢出率相近，為其半生期較長所致；另外亦為疏水物質的芬殺松及其代謝物fenthion sulfoxide、甲基多保淨則檢出濃度及頻率均極低(分別為未檢出; 0.010±0.03 μg/L, 10.7%; 0.003±0.013 μg/L, 8.4%)。
在農業密集的支流和雨季，可以觀察到嘉磷塞與固殺草(即除草劑)的總和，和水質參數中的總磷與氨氮有著顯著的正相關性(Spearman correlation coefficient=0.7, p value<0.01)，因此推測農業活動主導此集水區之水質，此相關性亦可作為日後調查環境水體農藥依據，初步篩選、評估採樣點之必要性，可節省實地調查之成本。鑒於以上可知農藥在水庫集水區較有殘留之風險，且其毒性較高，本研究一併調查台灣南部主要水庫集水區、與台灣本島及離島經淨水程序處理之清水中的嘉磷塞、固殺草、甲基多保淨、芬殺松殘留，結果顯示，8個水庫皆未有農藥檢出，4個攔河堰中高屏堰及東港堰檢出5種農藥及代謝物，二者皆位於農業密集區之下游；而100間淨水廠中僅有2間淨水廠分別檢出固殺草及甲基多保淨，皆為夏季採集之樣品，再次驗證夏季為水中農殘的高峰期，以及密集農業區內水體易有農殘之風險。
Recently, the need for high quality finished water has brought the land-use management around reservoir catchment to the public attention. Human would impact the source water quality by different levels based on the types of activities. It is crucial for competent authority understand how human activities would affect the water quality in order to regulate the land use for pollution control. The objective of this study is to evaluate the impacts of anthropogenic sources on water quality around reservoir catchment area by monitoring the occurrence of selected contaminants, including four pesticides (glyphosate, glufosinate, fenthion and thiophanate-methyl) and their two metabolites (aminomethylphosphonic acid (AMPA) and fenthion sulfoxide), one antibiotic (oxytetracycline) and one endocrine disrupting substance (bisphenol A) to reflect the pollution from agricultural run-off, aquaculture wastes and domestic sewage, respectively. Basic water quality parameters were also acquired. Samples were collected monthly from March 2017 to February 2018 from the two tributaries (Wanglai Creek and Zhuoshui Creek) in Agondian reservoir catchment located in southern Taiwan.
Results (sample number N=119) showed that the occurrence of organic pollutants in surface water was mainly related to their chemical properties. Compounds with high water solubility were easily detected with ppb level concentration and high detection frequency, including glyphosate (0.23±0.57 μg/L, 32.8%), glufosinate (0.20±0.85 μg/L, 16.8%), AMPA (0.25±0.55 μg/L, 38.0%, N=78) and oxytetracycline (1.82±2.28 μg/L, 59.7%). By contrast, the hydrophobic compounds, thiophanate-methyl (0.003±0.013 μg/L, 8.4%) and fenthion sulfoxide (0.010±0.032 μg/L, 10.7%, N=56) existed only ppt level concentration, and for the fast-degrading compound, fenthion, no residue was observed. Bisphenol A is an exception with low detected concentration (0.035±0.076 μg/L) but high detection frequency 33.6% (comparable to glyphosate) which may be due to its hydrophobicity and longer half-life in the environment.
From spatial aspect, the distribution of the monitored organic pollutants occurred mainly corresponding to the ambient land use, so they could be used to trace the pollution source and hotspot. From the time perspective, the application of agrochemicals and manure is usually in spring and early summer. Water body became vulnerable to the surface runoff caused by high rainfall which is typical during summer in southern Taiwan. On the contrast, bisphenol A was prone to be diluted instead of being washing out from soil in wet season. In addition, in the hotspot of agricultural pollution and wet season, the sum of glyphosate and its derivative product glufosinate positively correlated to total phosphorus and ammonia nitrogen (Spearman correlation coefficient=0.7, p value<0.01), inferring that agriculture activity dominated the water quality in the study area. The observed correlation allow more effective allocation of resources in future monitoring programs and field inspections.
Considering the risk and toxicity of pesticides in reservoir water, the residue of those selected pesticides were also investigated in the surface water from other 8 reservoirs and 4 weirs and in the finished water from 100 water treatment plants in Taiwan. The results showed that 2 weirs were detected with five pesticides and metabolites and 2 finished water samples were detected with glufosinate and thiophanate-methyl which all occurred in summer. To sum up, pesticides pose higher risk in the water body nearby the agriculture activity in summer.
Chapter 1 Introduction 1
Chapter 2 Literature review 3
2-1 Pesticides 3
2-1-1 Glyphosate, AMPA and glufosinate 4
2-1-2 Fenthion and fenthion sulfoxide 5
2-1-3 Thiophanate-methyl 6
2-2 Antibiotic 6
2-3 Endocrine disrupting substance 7
Chapter 3 Materials and methods 9
3-1 Chemicals 9
3-2 Study area 9
3-2-1 Agondian reservoir 9
3-2-2 Drinking water 11
3-2-3 Surface water 12
3-3 Sampling period, collecting and pretreatment 12
3-4 Quantification 13
3-4-1 Instruments 13
3-4-2 Glyphosate, AMPA and glufosinate 13
3-4-3 Fenthion, fenthion sulfoxide and thiophanate-methyl 14
3-4-4 Oxytetracycline (OTC) 15
3-4-5 Bisphenol-A (BPA) 15
3-4-6 Analytical method validation 15
3-5 Collection of water quality parameters 16
Chapter 4 Results and discussions 17
4-1 Occurrence of organic pollutants in Agongdian reservoir catchment 17
4-2 Spatial aspect of organic pollutants in Agondian reservoir 20
4-2-1 Occurrence at different sampling sites 20
4-2-2 The relation between emerging contaminants and conventional water quality parameters from spatial aspect 23
4-3 Seasonal pattern of organic pollutants in Agondian reservoir 26
4-3-1 Occurrence in different seasons 26
4-3-2 The relation between emerging contaminants and conventional water quality parameters from time scale 30
4-4 Monitoring of pesticides in other surface water and finished water 33
4-4-1 The occurrence of pesticides in drinking water in Taiwan 33
4-4-2 The occurrence of pesticides in other reservoir in southern Taiwan 35
Chapter 5 Conclusion and suggestion 36
5-1 Conclusion 36
5-2 Suggestion 37
Appendix (A) Recovery rate 44
Appendix (B) Data of selected organic pollutants 45
Appendix (C) Data of water quality parameters 48
Appendix (D) Rainfall data from measure station in Agondian reservoir 51
Appendix (E) The influence of stream reach and basin on the relations between water quality and selected organic pollutants 52
Appendix (F) The influence of rainfall on the relations between water quality and selected organic pollutants 53
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