本文選題：河口 + 無機(jī)硫　； 參考：《中國(guó)科學(xué)院煙臺(tái)海岸帶研究所》2016年博士論文

【摘要】：無機(jī)硫化物是沉積物中最活躍的硫形態(tài)之一,其地球化學(xué)循環(huán)過程與沉積物中鐵、磷及部分金屬元素的地球化學(xué)行為密切相關(guān),其氧化還原過程等遷移轉(zhuǎn)換過程能夠在一定程度上直接影響沉積物中鐵和磷的形態(tài)、活性及其環(huán)境行為。入海河口往往是陸源污染入海的最后一道屏障,同時(shí)也是典型的生態(tài)敏感區(qū)和環(huán)境脆弱帶,因此探究重污染河口沉積物中無機(jī)硫化物的地球化學(xué)特征及其與鐵和磷的耦合機(jī)制,對(duì)于近海及全球的硫鐵磷循環(huán)機(jī)制的認(rèn)識(shí)與調(diào)控具有重要的意義。本文選取中國(guó)北方典型海岸帶重污染河口-煙臺(tái)魚鳥河河口不同類型沉積物為研究對(duì)象,按照不同季節(jié)采用薄膜擴(kuò)散梯度技術(shù)(DGT)等原位分析技術(shù)調(diào)查了河口沉積物中溶解性S~(2-)、Fe~(2+)和溶解態(tài)活性磷酸鹽(DRP)的時(shí)空分布特征及其動(dòng)態(tài)擴(kuò)散過程,充分認(rèn)識(shí)了這些沉積物孔隙水中S-Fe-P三者之間極為顯著的相互制約或促進(jìn)機(jī)制。本研究同時(shí)結(jié)合沉積物粒度、有機(jī)質(zhì)和固相無機(jī)硫化物、活性鐵和磷形態(tài)及無機(jī)硫化物與活性鐵和磷形態(tài)之間的相關(guān)性等數(shù)據(jù),對(duì)重污染河口沉積物中無機(jī)硫化物的地球化學(xué)特征及其與鐵和磷循環(huán)的耦合機(jī)制進(jìn)行了深入探討,進(jìn)一步明確了沉積物中S-Fe-P的循環(huán)耦合機(jī)制。除此之外,本研究還通過模擬實(shí)驗(yàn),基本掌握了模擬自然潮汐的海水浸沒和淡水浸沒過程的方法,并對(duì)潮汐交替對(duì)重污染河口沉積物中硫鐵磷地球化學(xué)循環(huán)的影響進(jìn)行了定量表征。本文主要得到如下結(jié)論:(1)對(duì)魚鳥河河口沉積物中溶解性S~(2-)的時(shí)空分布特征及其動(dòng)態(tài)擴(kuò)散過程的研究結(jié)果表明,魚鳥河沉積物富含有機(jī)質(zhì),且泥質(zhì)沉積物中有機(jī)質(zhì)含量顯著高于砂質(zhì)沉積物,有機(jī)質(zhì)的分布主要受細(xì)顆粒組分控制�；钚杂袡C(jī)質(zhì)是魚鳥河沉積物硫酸鹽還原的控制因素,泥質(zhì)沉積物硫酸還原作用顯著高于砂質(zhì)沉積物。沉積物表層和次表層硫酸鹽還原作用較強(qiáng),隨深度降低硫酸鹽還原作用減弱。潮間帶沉積物富含可利用性硫酸鹽和活性有機(jī)質(zhì),硫酸鹽還原速率較高。淡水沉積物缺少可利用性硫酸鹽,硫酸鹽還原速率較低,沉積物中溶解性S~(2-)維持相對(duì)穩(wěn)定的平衡狀態(tài)。(2)魚鳥河河口沉積物中無機(jī)硫化物的時(shí)空分布特征和轉(zhuǎn)化機(jī)制的研究結(jié)果表明,魚鳥河河口沉積物硫酸鹽還原作用較強(qiáng),還原性無機(jī)硫化物(RIS)在沉積物表層和次表層以酸可揮發(fā)性硫化物(AVS)為主,而在沉積物深處則以黃鐵礦(CRS)為主。AVS和溶解性S~(2-)之間具有顯著的相關(guān)性,即AVS中溶解性S~(2-)含量較高,表明魚鳥河河口沉積物無機(jī)硫化物的活性和生物毒性較高。低黃鐵礦化度(DOP)和高AVS/CRS值表明活性鐵氧化物是硫酸鹽還原產(chǎn)物H2S向FeS轉(zhuǎn)化的主要限制因素,而元素硫(ES)是AVS向CRS轉(zhuǎn)化的主要限制因素。無機(jī)硫化物地球化學(xué)循環(huán)受季節(jié)性變化影響顯著,夏秋季節(jié)高溫促進(jìn)硫酸鹽的還原,從而使溶解性S~(2-)和AVS積累量增加;冬春季節(jié)低溫限制硫酸鹽的還原,導(dǎo)致溶解性S~(2-)和AVS積累量降低。夏季沉積物中ES含量和黃鐵礦化程度顯著高于冬季,且黃鐵礦化主要以多硫化方式進(jìn)行。(3)由魚鳥河河口沉積物中溶解性Fe~(2+)和活性鐵的時(shí)空分布特征得知,河口沉積物中溶解性Fe~(2+)和活性鐵的含量較低。較高的硫化程度(DOS)表明積物中鐵主要以FeS或FeS_2為主,鐵的硫化程度極高�；钚澡F氧化物是魚鳥河河口沉積物硫酸鹽還原產(chǎn)物H_2S向FeS轉(zhuǎn)化的主要限制因素。鐵的異化還原過程和化學(xué)還原過程同時(shí)存在,但以化學(xué)還原為主,即硫酸鹽還原產(chǎn)生的H_2S優(yōu)先還原鐵氧化物生成穩(wěn)定的黃鐵礦,限制了無機(jī)硫化物和鐵的活性。(4)由魚鳥河河口沉積物中溶解態(tài)活性磷酸鹽(DRP)和磷形態(tài)的時(shí)空分布特征得知,魚鳥河沉積物中的磷以鐵結(jié)合態(tài)磷(Fe-P)和有機(jī)磷(OP)為主,兩者占總磷含量的80%以上,可交換態(tài)磷(Ex-P)和鈣磷(Ca-P)的含量較低。冬季Fe-P和OP的含量顯著高于夏季,硫酸鹽還原和鐵氧化物還原是魚鳥河沉積物Fe-P季節(jié)性變化的主要控制因素,微生物的活性則是沉積物OP季節(jié)性變化的主要控制因素。(5)通過對(duì)魚鳥河河口沉積物無機(jī)硫化物循環(huán)與鐵和磷的循環(huán)耦合機(jī)制的初步研究的結(jié)果表明,重污染河口富含活性有機(jī)質(zhì)和可利用性硫酸鹽,硫酸鹽還原速率較高,硫酸鹽還原產(chǎn)物H_2S使活性鐵氧化物發(fā)生化學(xué)還原,生成FeS或FeS_2,限制了無機(jī)硫化物和鐵的活性。隨著鐵氧化物的還原溶解,被鐵氧化物吸附固定的磷酸鹽重新釋放。由于潮汐交替過程中存在鹽度差,導(dǎo)致河口沉積物-上覆水之間溶解性物質(zhì)交換擴(kuò)散通量升高,溶解性磷酸鹽由沉積物擴(kuò)散遷移至上覆水體中,提高了水體中磷的生物可利用性,增加了河口和近海水體富營(yíng)養(yǎng)化的風(fēng)險(xiǎn)。
[Abstract]:Inorganic sulfide is one of the most active sulfur forms in the sediments. Its geochemical cycle is closely related to the geochemical behavior of iron, phosphorus and some metal elements in the sediments. The transformation process, such as redox process, can directly affect the form, activity and environmental behavior of iron and phosphorus in the sediments. The sea mouth is often the last barrier of land source pollution to the sea, and it is also a typical ecological sensitive zone and environmental fragile zone. Therefore, it is important to explore the geochemical characteristics of inorganic sulfide and the coupling mechanism of iron and phosphorus in the sediments of the heavily polluted estuary, which is important for the understanding and regulation of the mechanism of the circulation of iron and phosphorus in the near sea and the world. In this paper, the different types of sediment in the estuary of the Yantai fish bird River, the heavily polluted estuary of the typical coastal zone of northern China, were studied. The temporal and spatial distribution of dissolved S~ (2-), Fe~ (2+) and dissolved active phosphate (DRP) in the estuarine sediments was investigated by using the in-situ analysis technique of film diffusion gradient (DGT) in different seasons. This study combines sediment granularity, organic matter and solid inorganic sulfides, the form of active iron and phosphorus, and the correlation between the inorganic sulphides and the forms of the active iron and phosphorus in the sediments, and the dynamic diffusion process is fully recognized. The study is combined with the grain size, organic and solid inorganic sulphides, the form of active iron and phosphorus and the correlation between the inorganic sulphides and the forms of the active iron and phosphorus. The geochemical characteristics of inorganic sulfide and the coupling mechanism of the iron and phosphorus cycle in the sediments of the polluted estuaries are deeply discussed, and the cyclic coupling mechanism of S-Fe-P in the sediments is further clarified. The influence of the tidal alternation on the geochemical cycle of sulfur, iron and phosphorus in the sediments of the heavily polluted estuaries was quantitatively characterized. The main results were as follows: (1) the spatial and temporal distribution characteristics of dissolved S~ (2-) in the sediment of the fish and bird River Estuary and its dynamic diffusion process showed that the sediment of the fish and bird river was rich in machine and mud. The content of organic matter in the sediments is significantly higher than that of sandy sediments. The distribution of organic matter is mainly controlled by the fine particles. The active organic matter is the controlling factor of sulfate reduction in the sediment of the fish bird River, and the sulfate reduction of the muddy sediments is significantly higher than that of the sandy sediments. Low sulfate reduction. Intertidal sediments are rich in available sulfate and active organic matter, with higher sulfate reduction rate. The lack of available sulphate in freshwater sediments, low sulfate reduction rate and relatively stable S~ (2-) in sediments. (2) inorganic sulphide in the sediments of the fish bird River Estuary The spatial and temporal distribution characteristics and transformation mechanism of the sediment show that the sulfate reduction of the sediment is stronger in the estuary of the fish and bird River, and the reductive inorganic sulfide (RIS) is dominated by acid volatile sulfide (AVS) in the surface and subsurface of the sediment, while in the depth of the sediment, there is a significant difference between the.AVS and the dissolved S~ (2-) of the pyrite (CRS). The high content of dissolved S~ (2-) in AVS indicates that the activity and biological toxicity of inorganic sulfide in the sediment of the fish and bird River estuary are higher. The low pyrite salinity (DOP) and high AVS/CRS value indicate that the active iron oxide is the main limiting factor for the transformation of the sulfate reduction product H2S into FeS, and the elemental sulfur (ES) is the main restriction of AVS to CRS transformation. Factors. The geochemical cycle of inorganic sulfides is significantly affected by seasonal changes. In summer and autumn season, high temperature promotes the reduction of sulfate, which makes the accumulation of dissolved S~ (2-) and AVS increase. In winter and spring, low temperature limits the reduction of sulphate, resulting in the decrease of the accumulation of dissolved S~ (2-) and AVS. The content of ES and the degree of pyrite mineralization in the summer sediments are significant. (3) the spatial and temporal distribution of dissolved Fe~ (2+) and active iron in the sediments of the estuary of the fish and bird river has been found to be higher than that in winter. The content of dissolved Fe~ (2+) and active iron in the estuarine sediments is lower. The higher vulcanization degree (DOS) indicates that the iron is mainly FeS or FeS_2, and the degree of iron vulcanization. Active iron oxide is the main limiting factor for the conversion of sulfate reduction product H_2S to FeS in the sediment of the fish and bird River Estuary. The process of dissimilation reduction and chemical reduction of iron exists simultaneously, but the chemical reduction mainly, that is, the H_2S preferential reduction iron oxide produced by sulfate reduction, produces a stable pyrite, which restricts the inorganic sulfide. (4) the spatial and temporal distribution of dissolved active phosphate (DRP) and phosphorus in the sediments of the fish bird River Estuary showed that the phosphorus in the sediment of the fish and bird river was dominated by iron bound phosphorus (Fe-P) and organophosphorus (OP), which accounted for more than 80% of the total phosphorus content, and the content of exchangeable phosphorus (Ex-P) and calcium phosphorus (Ca-P) was lower. In winter, the contents of Fe-P and OP in the sediments were low. The amount of sulphate reduction and iron oxide reduction is the main controlling factor for the seasonal variation of Fe-P in the sediment of the yubird River, and the activity of microorganism is the main controlling factor for the seasonal change of the sediment OP. (5) through the preliminary study on the cyclic coupling mechanism of the inorganic sulfides in the sediment of the fish and bird River Estuary with iron and phosphorus The results show that the heavy polluted estuary is rich in active organic matter and available sulphate, and the rate of sulfate reduction is higher. The sulfate reduction product H_2S makes the active iron oxide chemical reduction, producing FeS or FeS_2, limiting the activity of inorganic sulphides and iron. Salt is released again. Due to the difference of salinity in the process of tidal alternation, the exchange and diffusion flux of dissolved matter between the sediment and the overlying water in the estuary is increased, and the dissolved phosphate is transferred from the sediment to the overlying water body, which increases the bioavailability of phosphorus in the water body and increases the risk of eutrophication in the estuarine and offshore waters.

【學(xué)位授予單位】：中國(guó)科學(xué)院煙臺(tái)海岸帶研究所
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：X55;X52

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 王忍;李大鵬;黃勇;劉焱見;陳俊;;物理和生物組合擾動(dòng)對(duì)底泥微界面過程的影響[J];環(huán)境科學(xué);2015年11期

2 陳靜;孫琴;姚羽;丁士明;王沛芳;;DGT和傳統(tǒng)化學(xué)法比較研究復(fù)合污染土壤中Cd的生物有效性[J];環(huán)境科學(xué)研究;2014年10期

3 劉義;;土壤/沉積物中氧化物對(duì)磷和重金屬行為的影響[J];四川林業(yè)科技;2014年03期

4 郭連文;陳宏;姜玉花;張洋洋;薄樂;勵(lì)建榮;;薄膜梯度擴(kuò)散技術(shù)在重金屬植物有效性研究中的應(yīng)用[J];食品工業(yè)科技;2014年05期

5 張生銀;李雙林;董賀平;趙青芳;張中寧;史基安;;南黃海中部表層沉積物有機(jī)質(zhì)分布與分子組成研究[J];沉積學(xué)報(bào);2013年03期

6 朱茂旭;范長(zhǎng)清;楊桂朋;李鐵;;東海沉積物中鐵(Ⅲ)氧化物還原活性的動(dòng)力學(xué)表征[J];海洋學(xué)報(bào)(中文版);2012年04期

7 呂仁燕;朱茂旭;李鐵;楊桂朋;鄧霏霏;;東海陸架泥質(zhì)沉積物中固相Fe形態(tài)及其對(duì)有機(jī)質(zhì)、Fe、S成巖路徑的制約意義[J];地球化學(xué);2011年04期

8 朱茂旭;史曉寧;楊桂朋;李鐵;呂仁燕;;海洋沉積物中有機(jī)質(zhì)早期成巖礦化路徑及其相對(duì)貢獻(xiàn)[J];地球科學(xué)進(jìn)展;2011年04期

9 高海鷹;劉韜;丁士明;白秀玲;李寶;;滇池沉積物有機(jī)磷形態(tài)分級(jí)特征[J];生態(tài)環(huán)境;2008年06期

10 蒲曉強(qiáng);鐘少軍;劉飛;徐麗君;瞿成利;劉剛;陶小晚;;冷擴(kuò)散法提取沉積物中的酸可溶硫化物及其在中國(guó)邊緣海區(qū)的應(yīng)用[J];海洋科學(xué);2006年11期

相關(guān)碩士學(xué)位論文 前5條

1 張璐;膠州灣沉積物中硫酸鹽還原和鐵異化還原的影響因素研究[D];中國(guó)海洋大學(xué);2014年

2 李君;氮肥增效劑（NBPT/Nitrapyrin）對(duì)土壤氮素轉(zhuǎn)化及滴灌麥田N_2O排放的影響[D];石河子大學(xué);2014年

3 胡姝;江蘇濱海潮灘沉積物中還原無機(jī)硫和重金屬的形態(tài)特征[D];復(fù)旦大學(xué);2012年

4 周桂平;崇明東灘沉積物中還原無機(jī)硫（RIS）的形態(tài)特征及其轉(zhuǎn)化機(jī)制研究[D];復(fù)旦大學(xué);2011年

5 趙佳佳;海洋沉積物中異化Fe（Ⅲ）還原特征及鐵還原菌的分離鑒定[D];西北農(nóng)林科技大學(xué);2010年

，

本文編號(hào)：1833824