本文選題：巖溶地下河 + 多環(huán)芳烴　； 參考：《西南大學(xué)》2014年博士論文

【摘要】：巖溶地下水資源對(duì)我國西南巖溶區(qū)的重要性不言而喻,然而隨著社會(huì)經(jīng)濟(jì)快速發(fā)展和城市化進(jìn)程的加快,我國西南巖溶區(qū)水環(huán)境問題日益突出。這不僅與人類活動(dòng)有關(guān),同時(shí)也與巖溶環(huán)境本身的脆弱性密切相關(guān)。多環(huán)芳烴(PAHs)是一類持久性有機(jī)污染物(POPs),普遍存在于環(huán)境介質(zhì)中,其主要來自能源的燃燒。由于其具有毒性、能致癌、致突變而受到廣泛關(guān)注。一旦進(jìn)入巖溶環(huán)境有可能成為其最終歸宿,危害巖溶生態(tài)系統(tǒng)和人類健康。為此,弄清巖溶地下河系統(tǒng)多環(huán)芳烴的來源、組成特征、環(huán)境行為、遷移和分配過程及生態(tài)風(fēng)險(xiǎn),有助于提高對(duì)多環(huán)芳烴在巖溶地下河系統(tǒng)的污染機(jī)理的認(rèn)識(shí),具有重要意義。 本論文以重慶市南山老龍洞地下河系統(tǒng)為例,通過野外巖溶水文地質(zhì)和污染源地面調(diào)查,野外定位觀測(cè)、降雨期間采樣監(jiān)測(cè),利用氣相色譜—質(zhì)譜聯(lián)用儀為主要分析測(cè)試手段,以地下河及其地表污染來源為主線,研究多環(huán)芳烴在土壤、地表水、懸浮顆粒物、地下水、沉積物中的分布和污染特征及來源,分析多環(huán)芳烴在地下河中多相分配及影響因素,探討多環(huán)芳烴在巖溶地下河系統(tǒng)中的遷移傳輸過程。結(jié)果分析表明： 1、地下河流域環(huán)境介質(zhì)中PAHs含量、組成及污染水平。老龍洞流域表層土壤PAHs總量變化范圍為277～3301ng/g,平均值為752.6±635.5ng/g,其組成以2-3環(huán)為主。其中7種致癌性PAHs總量平均占到∑PAHs的36.17%。土壤有機(jī)質(zhì)(SOM)可能是影響PAHs含量的主要因素。受污水、季節(jié)的影響及不同PAH化合物的性質(zhì)差異,水中]PAHs含量和組成呈現(xiàn)不同的變化特征。與溶解態(tài)PAHs相比,地下河顆粒態(tài)PAHs含量較低,表現(xiàn)為雨季水中賦存于顆粒物上的PAHs含量高于旱季,主要與顆粒物的來源和性質(zhì)有關(guān)。流域內(nèi)水中PAHs以及懸浮顆粒物結(jié)合的PAHs組成均以低環(huán)為主,而高環(huán)PAHs幾乎未檢測(cè)到,這與低環(huán)溶解性相對(duì)較高有關(guān)。相對(duì)于溶解態(tài)PAHs,沉積物中,高環(huán)PAHs的比重相對(duì)富集,表明隨著分子量的增大,PAHs化合物傾向于吸附在顆粒物上 根據(jù)Mali szewska-Kordybach制定的土壤PAHs污染標(biāo)準(zhǔn),研究區(qū)表層土壤PAHs污染水平分別達(dá)到輕、中等和重污染水平,其中大部分為中等污染水平；根據(jù)Baumard等的劃分標(biāo)準(zhǔn),老龍洞地下河沉積物PAHs污染處于中等到高污染水平。按照荷蘭地下水水質(zhì)標(biāo)準(zhǔn)和加拿大水質(zhì)標(biāo)準(zhǔn),老龍洞流域水中PAHs以低環(huán)污染為特征；而以PAHs總量來看,地下河流域水中PAHs污染只有少數(shù)月份超出中國飲用水標(biāo)準(zhǔn)。與其他地區(qū)河流相比地下河PAHs污染水平居中,但巖溶區(qū)特殊的形態(tài)和環(huán)境有利于富集PAHs等持久性有機(jī)污染物,應(yīng)該引起足夠的重視。 根據(jù)地下河潛在來源水中PAHs分子量特征及PAHs同分異構(gòu)體比值解析表明,流域內(nèi)水中PAHs主要來自于石油源；綜合運(yùn)用PAHs分子量特征比值、同分異構(gòu)體比值和主成分/多元線性回歸分析表明,流域內(nèi)土壤PAHs污染主要來自交通排放與煤炭、石油及生物質(zhì)的燃燒源和石油產(chǎn)品泄漏的混合源,其中來自于燃燒源占56.4%,而石油源占到43.6%。 2、巖溶地下河PAHs多相分配及影響因素。研究表明有機(jī)質(zhì)是控制老龍洞地下河水相、沉積物、顆粒物中PAHs的行為和歸宿的重要的因素。其中溶解性有機(jī)碳(DOC)、有機(jī)碳(TOC)與PAHs的關(guān)系相對(duì)明確,而與顆粒物有機(jī)碳(POC)的關(guān)系比較復(fù)雜。溶解性有機(jī)質(zhì)(DOM)能夠促進(jìn)和積累低環(huán)的溶解態(tài)PAHs,是影響溶解態(tài)PAHs含量的主要因素,同時(shí)是高環(huán)PAHs重要的貯存庫。懸浮顆粒物(SPM)是影響溶解態(tài)PAHs含量的因素之一。與溶解相PAHs有所不同,顆粒物有機(jī)質(zhì)(POM)對(duì)PAHs的影響不顯著,主要是因?yàn)榇嬖贒OM等膠體物質(zhì)的影響。老龍洞地下河沉積物TOC與總PAHs含量成顯著正相關(guān),表明了沉積物有機(jī)質(zhì)是影響沉積物PAHs含量的主要因素,但I(xiàn)nP、DaA和BgP與TOC并不顯著相關(guān)。說明除了有機(jī)質(zhì)外,還有另外的因素在影響沉積物PAHs的含量,需要更為詳細(xì)的分析。 通過研究表明顆粒相—水相PAHs分配系數(shù)與POC無關(guān)系,而懸浮顆粒物對(duì)分配系數(shù)有顯著影響,原因是懸浮顆粒物濃度能夠帶來更多的DOC,導(dǎo)致DOM與POM相互競爭吸附PAHs。通過研究PAHs在沉積物—水相間的分配,獲得了表征有機(jī)碳?xì)w一化的分配系數(shù)Koc與辛醇-水分配系數(shù)Kow之間的線性自由能方程。發(fā)現(xiàn)地下河沉積物對(duì)PAHs化合物的親脂性較差。 3、巖溶地下河系統(tǒng)PAHs遷移傳輸過程。老龍洞地下河水與流域內(nèi)其它水中PAHs相似的組成特征,示蹤試驗(yàn)和不同水之間PAHs含量關(guān)系表明了巖溶形態(tài)對(duì)地下河系統(tǒng)PAHs的遷移有重要的作用。通過地下河上游與下游PAHs含量及組成比較發(fā)現(xiàn)2-3環(huán)PAHs表現(xiàn)為遠(yuǎn)距離遷移,而4-6環(huán)PAHs親顆粒性高,溶解性低,容易被沉積物或者碳酸鹽巖吸附,遷移能力不足。多環(huán)芳烴在地表土壤和地下河沉積物間的交換模式表明,地下河出口沉積物主要來源于上游水體傳輸及地表土壤的輸入。 降雨監(jiān)測(cè)表明,降雨期間落水洞的水輸入和地表水滲入是控制PAHs遷移過程的主要因素,不同結(jié)合態(tài)的PAHs受控于水動(dòng)力條件。降雨能夠促進(jìn)地下河系統(tǒng)PAHs由地表向地下遷移,而且流量越大,遷移量越大,一旦有足夠的雨強(qiáng),不僅帶來更多的懸浮顆粒物,而且使高環(huán)PAHs更容易遷移,同時(shí)遷移過程中受DOC、POC、懸浮顆粒物濃度及顆粒物本身的種類和性質(zhì)的影響,使得PAHs在各相中的分配產(chǎn)生差異。 4、巖溶地下河流域PAHs的生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)。運(yùn)用風(fēng)險(xiǎn)商值(RQ)法對(duì)水中PAHs生態(tài)風(fēng)險(xiǎn)進(jìn)行評(píng)價(jià),結(jié)果發(fā)現(xiàn)在檢測(cè)到的PAH化合物的生態(tài)風(fēng)險(xiǎn)水平處于中等污染和重污染風(fēng)險(xiǎn)。以總PAHs來看,桂花灣泉和老龍洞地下河出口達(dá)到高風(fēng)險(xiǎn)等級(jí),已嚴(yán)重污染；趙家院子泉和地表水處于中等風(fēng)險(xiǎn)2級(jí)別。老龍洞沉積物PAHs處于低風(fēng)險(xiǎn)水平,很少產(chǎn)生負(fù)面生態(tài)效應(yīng),而仙女洞PAHs污染存在較高的生態(tài)風(fēng)險(xiǎn),這與ERL/ERM和TEL/PEL法,平均效應(yīng)區(qū)間中值商法(M-ERM-Q)評(píng)價(jià)結(jié)果基本一致。土壤PAHs污染為中等風(fēng)險(xiǎn)。老龍洞流域水中3環(huán)PAHs對(duì)生態(tài)壓力貢獻(xiàn)較大,而土壤和沉積物中2環(huán)和3環(huán)貢獻(xiàn)較大,因此需要采取有效措施減少2-3環(huán)PAHs的污染。 表層巖溶系統(tǒng)由于土層薄,巖溶裂隙發(fā)育,利于PAHs進(jìn)入表層泉,導(dǎo)致桂花灣泉和趙家院子泉PAHs污染仍存在較高的生態(tài)風(fēng)險(xiǎn)。黃桷埡污水切斷前后,老龍洞水PAHs污染分別處于高風(fēng)險(xiǎn)和中等風(fēng)險(xiǎn)狀態(tài)。地下河的補(bǔ)給來源的介質(zhì)中PAHs污染的生態(tài)風(fēng)險(xiǎn)越高,地下河中PAHs污染的生態(tài)風(fēng)險(xiǎn)也越高。不同分子量PAHs遷移行為的差異,導(dǎo)致老龍洞地下河上游和下游生態(tài)風(fēng)險(xiǎn)水平在水中和沉積物中有所差異,高環(huán)PAHs富集在地下河管道,其在逐漸往下游遷移過程中,將對(duì)下游的生態(tài)構(gòu)成威脅。
[Abstract]:With the rapid development of the social economy and the acceleration of the urbanization process , the water environmental problems of the karst area in the southwest of China are becoming more and more serious .

In this paper , the distribution and pollution characteristics and source of polycyclic aromatic hydrocarbons ( PAHs ) in soil , surface water , suspended particulate matter , groundwater and sediment are studied by using gas chromatography - mass spectrometry ( GC - MS ) as an example , and the distribution and pollution characteristics and source of polycyclic aromatic hydrocarbons ( PAHs ) in soil , surface water , suspended particulate matter , groundwater and sediment are studied by gas chromatography - mass spectrometry ( GC - MS ) .

Soil organic matter ( SOM ) is the main factor affecting the content of PAHs .

According to the soil PAHs pollution standard , the level of PAHs pollution in the surface layer of the study area reached light , medium and heavy pollution levels , most of which were medium pollution levels .
According to the classification standard of Baumard et al . , the PAHs pollution in the old Longdong underground river sediments is at medium to high pollution level . According to the water quality standard of the Netherlands and the Canadian standard of water quality , the PAHs in the water of the old Longdong basin are characterized by low ring pollution ;
The PAHs pollution in the groundwater basin is only a few months beyond the standard of drinking water in China . The PAHs pollution level in the underground river is centered in comparison with the rivers in other areas . However , the special morphology and environment of karst area are conducive to the enrichment of persistent organic pollutants such as PAHs , which should be paid enough attention .

The analysis of the molecular weight of PAHs and the ratio of PAHs in potential source water in the base area indicates that the PAHs in the water in the basin are mainly from petroleum sources ;
Based on the analysis of the ratio of the molecular weight of PAHs , the ratio of isomers and the principal component / multivariate linear regression analysis , the PAHs pollution in the basin mainly comes from the mixed source of the traffic emission and the combustion sources of coal , oil and biomass and the leakage of petroleum products , of which 56.4 % of the sources are from the combustion source and 43.6 % of the petroleum sources .

Dissolved organic carbon ( DOC ) , organic carbon ( TOC ) and PAHs are the main factors influencing the content of PAHs in sediments .

It is shown that the distribution coefficient of PAHs in the particulate phase - water phase has no relation with POC , and the suspended particulate matter has a significant influence on the distribution coefficient because the concentration of suspended particles can bring more DOC , which leads to the competition between DOM and POM .

3 . PAHs migration transmission process in karst underground river system . The relationship of PAHs content between the underground river and other water in the basin indicates that the karst morphology plays an important role in the migration of PAHs in the underground river system . By comparison of the content and composition of PAHs in the upper and lower reaches of the underground river , it is found that the 2 - 3 - ring PAHs show a long - distance migration , while the 4 - 6 - ring PAHs have high affinity , low solubility , easy to be adsorbed by sediments or carbonate rocks , and the migration ability is insufficient . The exchange pattern between the surface soil and the underground river sediments indicates that the sediments of the underground river are mainly derived from the transmission of the upstream water body and the input of surface soil .

Rainfall monitoring indicates that the water input and surface water infiltration during rainfall are the main factors controlling the migration process of PAHs . PAHs in different binding sites are controlled by hydrodynamic conditions . The larger the flow rate , the greater the migration volume , the greater the flow rate , the greater the migration volume , and the influence of DOC , POC , suspended particulate matter concentration and the kind and nature of the particulate matter in the course of migration , so that the distribution of PAHs in each phase is different .

4 . The ecological risk assessment of PAHs in the karst underground river basin was evaluated . The ecological risk of PAHs in water was evaluated by using the method of risk quotient . The results showed that the ecological risk level of PAH compounds was at medium pollution and heavy pollution risk .
The PAHs in the old Longdong basin have a higher ecological risk than that of the ERL / ERM and TEL / PELLmethods . The PAHs in the old Longdong basin have a higher contribution to the ecological pressure , while the 2 and 3 rings in the soil and sediment contribute more . Therefore , effective measures are needed to reduce the pollution of 2 - 3 PAHs .

The higher ecological risk of PAHs in the groundwater is higher . The higher the ecological risk of PAHs pollution in the groundwater , the higher the ecological risk of PAHs pollution in the underground rivers .
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：X523;X824

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