本文選題：十溴聯(lián)苯醚 + 土壤��； 參考：《浙江大學(xué)》2017年博士論文

【摘要】：十溴聯(lián)苯醚(Deca-BDE)是目前廣泛使用的一種溴代阻燃劑,在環(huán)境中的檢出頻率和濃度呈逐年上升趨勢,所導(dǎo)致的環(huán)境污染問題倍受關(guān)注,已成為一種新型有機污染物。全面認識Deca-BDE在環(huán)境介質(zhì)中及生物體中的降解、轉(zhuǎn)化、蓄積、殘留規(guī)律,是正確認識和科學(xué)評價其環(huán)境行為與環(huán)境風(fēng)險性的基礎(chǔ),而上述科學(xué)問題的詮釋需要依賴同位素標(biāo)記化合物及其相應(yīng)的示蹤技術(shù)。然而,目前因缺乏標(biāo)記化合物制約了相關(guān)研究的深入開展。本論文在合成示蹤劑~(14)C-Deca-BDE的基礎(chǔ)上,采用碳-~(14)示蹤法系統(tǒng)研究了 Deca-BDE在土壤和土壤動物中的轉(zhuǎn)化和歸趨。為完整和正確的評價十溴聯(lián)苯醚在環(huán)境中的風(fēng)險提供依據(jù)。(1)利用放射性1MC標(biāo)記苯酚作為原料,優(yōu)化放射性中間產(chǎn)物二苯醚和放射性標(biāo)記~(14)C-Deca-BDE的合成路線及方法。其中,放射性中間產(chǎn)物標(biāo)記二苯醚的最佳投料量為碳酸銫(5.66 g,17.37 mmol)、溴化亞銅(0.~(14)78 g,1.03 mmol),2-環(huán)己酮甲酸乙酯(0.3311 g,9.73 mmol)、碘苯(1.699 g,8.32 mmol)和非標(biāo)記苯酚(0.7301 g,7.7 mmol),標(biāo)記苯酚(24.096 mg,0.251 mmol),最終獲得放射性中間產(chǎn)物二苯醚l.0177g。并利用放射性中間產(chǎn)物最終合成目標(biāo)化合物~(14)C-Deca-BDE,其最佳投料量為標(biāo)記中間產(chǎn)物二苯醚0.5311 g、溴素3 ml、二氯化碳3.5 mL、三氯化鋁0.25 g、反應(yīng)時間為7 h,最終獲得~(14)C-Deca-BDE 2.0788 g。并通過GC-MS、紅外和HPLC-LSC等定性定量手段,測定標(biāo)記化合物的結(jié)構(gòu)、化學(xué)純度(98.4%)、放射性純度(98.6%)和比活度為(1.25 mCi/mmol)。(2)充分發(fā)揮同位素示蹤技術(shù)的獨特優(yōu)勢,從質(zhì)量平衡和示蹤動力學(xué)角度,綜合考量Deca-BDE在土壤中的可提殘留量、結(jié)合殘留量和礦化動態(tài)規(guī)律。研究表明:在130 d的培養(yǎng)周期內(nèi),Deca-BDE在不同土壤類型、活性污泥改性土壤及滅菌土壤中很難降解、不易礦化,屬于典型的持久性有機污染物;其中,結(jié)合態(tài)殘留和可提態(tài)殘留在中性土壤黃泥田土(S-3)中分別為97.4%和2.6%;在酸性土壤紅砂田土(S-l)中分別為99.65%和0.35%;在堿性土壤淡涂泥田土(S-4)中分別為1.3%和98.7%;在滅菌活性污泥(添加比例為5%-20%)改性黃松土(S-2)中分別為0.79%-98.87%和1.13%-3.21%;在非滅菌活性污泥添加的改性黃松土(S-2)(滅菌和非滅菌)中分別為98.36%-98.53%和1.47%-1.64%;滅菌和非滅菌的黃松土(S-2)分別為98.4%-98.7%以及1.3%-1.6%。通過多組實驗闡明了Deca-BDE在土壤中的殘留主要以可提態(tài)形式存在,結(jié)合態(tài)殘留不足4%,且結(jié)合態(tài)殘留的形成量隨著土壤中有機質(zhì)含量和活性污泥添加而上升。進一步分析可提態(tài)殘留中的成分可知,土壤和活性污泥中的微生物并不是十溴聯(lián)苯醚降解的主要因素。(3)實驗分別從某地污水處理廠和電子拆解廠以及農(nóng)田中采集活性污泥和土壤樣品,從中富集、篩選出CZ-1、PT-12和HZ-4三株降解菌,并在20 mg/L的條件下分別測定其降解率分別為11.0%、15.82%和21.0 4%,故選用HZ-4(Rhodococcus erythropoli)(重新命名為 HNS209-1)作為研究對象,進行下一步研究。選取34種代表性藥物對其耐藥性進行檢測,結(jié)果表明;菌株HNS209-1對11種藥物較為敏感;對21種藥物具有一定的耐藥性;僅對兩種藥物有較強的耐藥性,且不會對異育銀鯽產(chǎn)生生物毒性。將十溴聯(lián)苯醚在添加到好氧土壤中發(fā)現(xiàn),菌株的添加導(dǎo)致黃松土(S-2)的結(jié)合殘留從0.45%上升到1.75%,但并沒有促進十溴聯(lián)苯醚在好氧土壤中的降解。(4)進一步將菌株添加到土壤-蚯蚓的生物系統(tǒng)中,以研究降解菌株對于蚯蚓以及土壤中十溴聯(lián)苯醚的影響。實驗表明在35天的培養(yǎng)周期內(nèi)十溴聯(lián)苯醚沒有發(fā)生顯著地降解。在添加有蚯蚓的土壤中十溴聯(lián)苯醚的結(jié)合殘留2.5%,仍顯著地高于不加蚯蚓的土壤。在所有處理中土壤中的十溴聯(lián)苯醚均會被蚯蚓吸收,但由于蚯蚓生物富集系數(shù)值較小(BSAF ≤ 0.31),其體內(nèi)十溴聯(lián)苯醚不會進行生物富集。此外,通過放射自顯影技術(shù)對蚯蚓體內(nèi)吸收的十溴聯(lián)苯醚的分布作出研究發(fā)現(xiàn)其分布規(guī)律為砂囊消化系統(tǒng)頭部尾巴體壁。且十溴聯(lián)苯醚降解菌株HNS209-1并沒有顯著地影響蚯蚓的生物富集和土壤中十溴聯(lián)苯醚的環(huán)境行為。另值得注意的是,蚯蚓所吸收十溴聯(lián)苯醚總量的近三分之一是以結(jié)合態(tài)殘留形式存在于體內(nèi),該結(jié)果證實了以可提態(tài)為基礎(chǔ)的傳統(tǒng)研究嚴重低估了十溴聯(lián)苯醚在蚯蚓體內(nèi)的真實濃度,換言之,傳統(tǒng)的基于可提態(tài)的生物富集和環(huán)境評價手段急需進一步改進,且存在于蚯蚓腸道中的十溴聯(lián)苯醚的含量需要引起足夠的重視。
[Abstract]:Ten brominated diphenyl ether (Deca-BDE) is a kind of brominated flame retardant widely used at present. The detection frequency and concentration in the environment are increasing year by year. The environmental pollution problem caused by Deca-BDE has become a new kind of organic pollutant. It is a comprehensive understanding of the degradation, transformation, accumulation and residue law in the environment medium and the organism. It is the basis for the correct understanding and scientific evaluation of its environmental behavior and environmental risk, and the interpretation of the above scientific problems needs to be dependent on isotopic markers and their corresponding tracing techniques. However, the lack of labeled compounds restricts the development of related research. The carbon ~ (14) tracer system was used to study the transformation and convergence of Deca-BDE in soil and soil animals. It provides a basis for a complete and correct evaluation of the risk of ten brominated diphenyl ethers in the environment. (1) using the radioactive 1MC labeled phenol as a raw material, the synthesis route of radioactive intermediate product two benzyl ether and radioactive labeling ~ (14) C-Deca-BDE is optimized. Among them, the optimal dosage of radioactive intermediate products marked two benzyl ether is cesium carbonate (5.66 g, 17.37 mmol), copper bromide (0.~ (14) 78 g, 1.03 mmol), 2- cyclohexanone formate (0.3311 g, 9.73 mmol), iodine benzene (1.699 g, 8.32 mmol) and non labeled phenol (0.7301 g, 7.7 mmol), and phenol (24.096, 7.7 mmol), and finally to obtain radiation. The intermediate product of the intermediate product, two benzyl ether l.0177g., finally synthesized the target compound ~ (14) C-Deca-BDE with a radioactive intermediate product, and its optimum feeding amount was the intermediate product two benzyl ether 0.5311 g, bromine 3 ml, two chlorinated carbon 3.5 mL, aluminum trichloride 0.25 g, reaction time 7 h, and eventually obtained ~ (14) C-Deca-BDE 2.0788 g. and passed GC-MS, infrared and HPLC-LSC. Determine the structure of the labeled compounds, chemical purity (98.4%), radioactivity purity (98.6%) and specific activity (1.25 mCi/mmol). (2) give full play to the unique advantages of isotopic tracer technology. From the angle of mass balance and tracer dynamics, the residual amount of Deca-BDE in the soil, the residual amount and the mineralization dynamics are combined. The study showed that in the culture period of 130 D, Deca-BDE was difficult to degrade in different soil types, activated sludge modified soil and sterilized soil, which was not easily mineralized, which belonged to typical persistent organic pollutants; among them, the residual and extractable residues were 97.4% and 2.6% in the neutral soil (S-3), and in the acid soil. The red sand field soil (S-l) is 99.65% and 0.35%, respectively, 1.3% and 98.7% in alkaline soil (S-4), and 0.79%-98.87% and 1.13%-3.21% in the modified activated sludge (5%-20%) modified pine soil (S-2), respectively, in the modified Huang Songtu (S-2) (sterilization and non sterilizing) added by non sterilizing activated sludge as 98.36%-, respectively. 98.53% and 1.47%-1.64%; sterilization and non sterilizing Huang Songtu (S-2), respectively, 98.4%-98.7% and 1.3%-1.6%. through a number of experiments to clarify that the residues of Deca-BDE in the soil are mainly in the form of extractable state, and the residual state residues are less than 4%, and the formation of the residual state residues is increased with the content of organic matter in the soil and the addition of activated sludge. Microorganism in soil and activated sludge is not the main factor for the degradation of ten brominated diphenyl ethers. (3) the experiments were collected from a sewage treatment plant and electronic dismantling plant and in the farmland to collect active sludge and soil samples, and three strains of CZ-1, PT-12 and HZ-4 were screened and 20 m were screened out. The degradation rate of g/L was 11%, 15.82% and 21.04% respectively, so HZ-4 (Rhodococcus erythropoli) (renamed HNS209-1) was selected as the research object, and the next study was carried out. 34 representative drugs were selected to detect the drug resistance. The results showed that the strain HNS209-1 was more sensitive to 11 drugs and 21 drugs. It has a certain resistance; it has strong resistance to two drugs and does not produce biotoxicity to the crucian carp. The addition of ten brominated diphenyl ethers to aerobic soil is found, and the addition of the strain leads to the increase of Huang Songtu's (S-2) binding residue from 0.45% to 1.75%, but it does not promote the degradation of ten brominated diphenyl ethers in aerobic soil. (4) The strain was further added to the soil earthworm biological system to study the effects of the degrading strains on the earthworms and the ten brominated diphenyl ethers in the soil. The experiment showed that the ten brominated diphenyl ethers did not degrade significantly during the 35 day incubation period. The remaining 2.5% of the ten brominated diphenyl ethers in the soil adding earthworms still significantly higher than not. Earthworms were added to the soil. Ten brominated diphenyl ethers were absorbed by earthworms in all treatments, but due to the smaller number of earthworm bioenrichment lines (BSAF < 0.31), ten brominated diphenyl ethers were not bioenriched. In addition, the distribution of ten brominated diphenyl ethers absorbed in earthworms was found by autoradiography. Ten bromo diphenyl ether degrading strain HNS209-1 did not significantly affect the bioaccumulation of earthworms and the environmental behavior of ten brominated diphenyl ethers in the soil. Furthermore, it is worth noting that nearly 1/3 of the total amount of ten brominated diphenyl ethers absorbed by earthworms exists in the form of binding state residues in the body. The results confirm that the traditional study based on the extractable state seriously underestimates the true concentration of ten brominated diphenyl ethers in the earthworms. In other words, the traditional methods of bioaccumulation and environmental assessment based on the extractable state need to be further improved, and the content of ten brominated diphenyl ethers in the earthworm intestines needs to be paid enough attention.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：X592

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