中国科学院生态环境研究中心机构知识库
Advanced  
RCEES OpenIR  > 环境水质学国家重点实验室  > 学位论文
题名: 基于液相31P-NMR技术与SMT方法的海河流域主要湿 地、河流沉积物中磷形态特征研究
作者: 李洁
学位类别: 硕士
答辩日期: 2015-05
授予单位: 中国科学院研究生院
授予地点: 北京
导师: 单保庆
关键词: 磷形态,沉积物,海河流域,SMT法,液相 31P-NMR,Phosphorus Compounds, Sediments, Haihe Basin,SMT,31P-NMR
其他题名: Detection of phosphorus components in the sediments of Haihe Basin by 31P-NMR and SMT
学位专业: 环境工程
中文摘要:     我国目前正处于经济高速增长期,富营养化问题是我国面临的最主要水污染问题之一。而海河流域由于其区位特殊,水资源匮乏,工业密集、城市密布,面临严重的环境问题,大量的氮、磷等营养物质和有机碳等化学耗氧物质排入河流,造成河流、湿地部分水质和底泥处于富营养化状态,进而给渤海带来诸如赤潮等严重的环境问题。
    本文选择 SMT方法和液相   31P-NMR技术研究了海河流域主要河流和湿地沉积物中磷形态特征。SMT法通过使用不同性质的酸碱提取剂将沉积物磷分为无机磷(IP),有机磷(OP),NaOH提取态磷(NaOH-P),HCl提取态磷(HCl-P)及总磷(TP),较好地将无机磷分为了较易释放的 NaOH-P以及稳定的  HCl-P,而SMT法只能得到有机磷总量,无法深入的认识有机磷。因此同时选择本组构建的适合于富含 Fe/Al的沉积物的有机磷液相31P-NMR分析方法测定沉积物中有机磷含量,这一方法具有提取效率高、稳定且图谱质量较好的优势,可以测定沉积物中不同有机磷化合物含量。本文利用这两种方法,分别对海河流域主要滨海湿地、主要入海河流沉积物的磷形态特征及其转化特征进行了探讨;为了进一步研究海河流域典型河流人工河流沉积物中磷形态特征,选择了永定河、永定新河以及子牙河、子牙新河对比分析了其磷形态空间分布特征,并对子牙新河沉积物中磷的沉积特征进行了深入的研究。通过系统的研究,不仅揭示了海河流域主要滨海湿地、入海河流沉积物的磷组成及含量特征,而且探讨了海河流域特有人工河流沉积物中磷形态分布及沉积特征,为海河流域河流富营养化治理提供了理论依据。研究结果表明:
(1)HCl-TP和EDTA-TP相关性显著,且回收率稳定在   50%以上,表明SMT分级方法和改进的液相31P-NMR分析方法都是科学有效的。沉积物中总共有六种磷化合物通过液相 31P-NMR被检测出来,正磷酸盐和磷酸单酯分别是沉积物中总磷和有机磷的主要组成成分,焦磷酸盐、DNA-P、磷脂、膦酸盐和多聚磷酸盐含量较低。
(2)湿地土壤中的磷主要是无机磷,且主要是不易释放的 HCl-P,较易释放的 NaOH-P比例只有  5%~22%,释放风险较小。有机磷的主要组分是磷酸单酯,且南部湿地土壤中有机磷含量明显高于北部湿地,在南部湿地发现含量较基于 SMT方法及液相31P-NMR技术的海河流域主要湿地、河流沉积物磷形态特征研究高的  DNA磷,说明其微生物活性较高。除此之外,在受到水产养殖污染的湿地,其有机磷含量会相对偏高,造成磷累积。
(3)由于海河流域污染较重,其流域内的三条河流滦河、永定新河、子牙新河总磷、有机磷、正磷酸盐含量都较高,有较高的释放风险。沿河流流向TP有降低趋势,并且 HCl-P含量在河口附近含量较高。
(4)人工河流子牙新河、永定新河沉积物中总磷、正磷酸盐、焦磷酸盐、磷酸单酯、DNA-P含量均明显高于自然河流子牙河、永定河,自然河流子牙河沿河流流向,总磷含量有明显的降低趋势。人工河流具有河道蜿蜒度小,河岸带形态单一,坡降小,闸坝多等特点,因此物理连续性差,自净能力弱,沉积物中磷含量较高,富营养化程度高。
(5)子牙新河沉积物中 TC、TN、TS、TP含量的垂向变化趋势基本一致,表层含量高,中上部出现一个速降层,而后逐渐波动降低,说明沉积物中的磷存在着表层富集的现象,大量污染物受沉积作用累积于上层。HCl-P所占比例随深度的增加有增加的趋势,NaOH-P与  HCl-P的变化趋势相反,随深度的增加而降低,OP所占TP比例最小,变化趋势和NaOH-P相似。随着沉积柱深度的增加,磷的种类和含量都逐步降低,子牙新河中下游样点总磷含量较高,且降低速率要明显大于中上游样点。中下游河段河流沉积物中有机磷含量呈现迅速的降低趋势,且表层沉积物磷含量可以达到 20 cm深度磷含量的十倍左右,反映了表层沉积物磷污染的严重性以及沉积物中磷释放的危险性。
英文摘要:     With  the  rapid  growth  of  the  world  population  and  economy,  the  growing pollution problem caused the  continued deterioration of the water quality, and  water environment has  become  a global  environmental problem.  China  is currently  in a period of  rapid economic  growth, and  eutrophication is one  of the  major pollution problems our  country faced. As  the Haihe  River Basin has  the special  location, its cities and industries  were intensive and  large amounts of nitrogen,  phosphorus, and other chemical  ozone-depleting substances were  discharged into the  rivers, causing part of  the water  and  sediments quality  of rivers,  wetlands in  eutrophic state,  and thus brought serious environmental problems to the Bohai Sea such as red tide.
    This paper  studied different phosphorus  components in the  sediments of  main rivers and wetlands  in the Haihe Basin by  using SMT and  31P-NMR methods. SMT is a sequential extraction procedure using different  extraction agents HCl and NaOH,and  sediment phosphorus  can  be  divided into  inorganic  phosphorus (IP),  organic phosphorus (OP), NaOH-P, HCl-P and TP. However,  SMT method only get the total organic phosphorus, and  unable to  understand  organic phosphorus  thoroughly.  So we selected  the  31P-NMR analysis  suitable for  Fe/Al-rich sediment  to measure the content  of  different organic  phosphorus  compounds  in  sediments.   31P-NMR  is a non-destructive,  non-invasive  technique  for  identifying  chemical  forms   and  can analysis  OP component  completely,  Therefore, it  is  an ideal  technique  for use  in analysis of OP species in marine or freshwater sediment.
    In  this   paper,  we   identified  the   phosphorus  components   distribution  and transformation characters of the major coastal wetlands and rivers respectively in the Haihe  River  Basin. In  order  to  further  study  the  unique  phosphorus distribution characteristics of  the artificial  river, we  selected the  Yongding River, Yongdingxin River and  Ziya  River, Ziyaxin  River  to analysis  the phosphorus  characteristics  in comparison; what’s more,  vertical change trends of  phosphorus fractions in Ziyaxin River sediment was  studied thoroughly. In all, we  not only revealed the content  and distribution characteristics of phosphorus composition of major coastal wetlands and rivers  in the  Haihe  River Basin,  but  also  explored the  unique  characteristics and vertical  change trends  of  phosphorus  fractions in  artificial  river sediments  in  the Haihe   River  Basin,   thus   provided   the   theory  basis   for   internal   control   for eutrophication of the Haihe River Basin.
The main contents and detail results are as follows:
(1) HCl-TP and  EDTA-TP were significantly correlated,  and the recovery  was stable  above  50%,  indicating  that  SMT  classification method  and  the  improved 31P-NMR methods were scientifically valid,  and can reflect the actual content  of the samples.  Six phosphorus  compounds  were  detected by   31P-NMR,  orthophosphate and phosphate  monoesters were  the main  components of  the total  phosphorus and organic   phosphorus   in   the   sediments,   what’s   more,   pyrophosphate,   DNA-P, phospholipids , phosphonates and polyphosphates content were relatively low.
(2) The phosphorus in  the wetlands soil was mainly  inorganic phosphorus, and most of it were HCl-P, the proportion of easy released NaOH-P was only 5%  to 22%,thus  had little  risk of  release.  The main  component  of the  organic  phosphorus is phosphate monoester, and the phosphate monoester content  in the southern wetlands was  higher  than  it  in  the  northern   wetlands;  DNA-P  presented  in  most  of  the southern  wetlands,  indicating  that  microbial  activity  was  higher  in  the southern wetlands. In addition, the wetlands subjected of  aquaculture pollution, had relatively high content of organic phosphorus, resulting in the accumulation of phosphorus.
(3) Due to heavy pollution in the Haihe River Basin, three rivers in it, including Luan River, Yongdingxin  River and Ziya River, all  had high content of phosphorus,organic phosphorus and  orthophosphate, thus had  a high risk of  release. TP content along  the  river flows  tended  to  decrease,  and  HCl-P content  in  the  estuary  was relatively high.
(4) The artificial river Ziyaxin River and Yongdingxin  River had a significantly higher content of phosphorus, orthophosphate, pyrophosphate, phosphate monoester,and DNA-P  than the natural  river Ziya  River and Yongding  River. Arificial  rivers had small degree of  meandering, simple riparian zone, small slope,  and many dams, so  their physical  continuity  were  poor, and  had  weak self-purification  capacities.Therefore,  the phosphorus  content in  sediments  of artificial  rivers were  relatively high, and had a high state of eutrophication.
(5) The vertical  trends of the  content of TC, TN,  TS, TP were similar,  and the content  in  the  surface  were  highest,  then  decreased  rapidly,  and  then  gradually reduced.  It  indicated that  the  phosphorus  enriched  in the  surface  sediments,  and large  quantities  of  pollutants accumulated  in  the  upper  layers.  HCl-P  proportion increased with  the depth,  and decreased quickly  in the  first 10 cm;  while NaOH-P had a  opposite variation trend  with the HCl-P,  and it  decreased with the  depth; OP shared smallest proportion of TP, and had a similar trend with the NaOH-P.
    With the  increased depth of  the column, the types  and contents of  phosphorus are gradually reduced. The phosphorus content  in the middle and downstream of the Ziyaxin   River  were   significantly  higher   than   the  upstream   samples.   Organic phosphorus content in the  middle and lower reaches  of the river sediment showed  a quickly decreasing  trend, and the  phosphorus content in  the surface  sediments was ten  times  than  it  in  the depth  of  20  cm  around,  it  indicated  the  seriousness  of phosphorus pollution  in  surface sediments,  and suggested  the  high release  risk  of phosphorus in sediments
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/34338
Appears in Collections:环境水质学国家重点实验室_学位论文

Files in This Item:
File Name/ File Size Content Type Version Access License
李洁--基于液相31P-NMR技术与SMT方法的海河流域主要湿 地、河流沉积物中磷形态特征研究.pdf(5311KB)学位论文--限制开放 联系获取全文

Recommended Citation:
李洁. 基于液相31P-NMR技术与SMT方法的海河流域主要湿 地、河流沉积物中磷形态特征研究[D]. 北京. 中国科学院研究生院. 2015.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[李洁]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[李洁]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Copyright © 2007-2018  中国科学院生态环境研究中心 - Feedback
Powered by CSpace