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贵州红枫湖、百花湖沉积物-水界面营养元素(磷、氮、碳)的生物地球化学作用
王雨春
2001
学位授予单位中国科学院地球化学研究所
学位授予地点中国科学院地球化学研究所
学位名称博士
学位专业环境地球化学
关键词湖泊(水库) 沉积物-水界面 生物地球化学作用(早期成岩作用) 营养元素 元素赋存形态分析 扩散通量 吸附解吸 “反应-扩散”模式 有机质降解
摘要富营养化是目前水资源管理的一个主要环境问题。水体中过量的营养元素是引起富营养化的根本原因,其中磷和氮是主要的控制因素。多数湖泊中磷是藻类自然生长的限制因子,因此多年来人们治理富营养化水体的主要策略是减少磷的排放,然而,通过此法成功恢复湖泊生态的例子屈指可数,一个主要的原因就是沉积物中的磷的再释放。因此,沉积物营养元素(尤其是沉积物-水界面上)的生物地球化学过程一直是湖泊科学研究的焦点。本次工作选择贵州的两个人工湖泊—红枫湖、百花湖,通过对磷、氮、碳在沉积物中的化学形态、垂直剖面等方面的研究,结合室内模拟实验和模式计算,揭示了沉积物早期成岩过程中磷、氮、碳的地球化学行为及其潜在的环境效应。尤其是对沉积物磷开展了较深入的研究。红枫湖、百花湖水体中的N/P为46~126,磷是湖泊的限制性营养因子。分析表明,红枫湖、百花湖沉积物中的全磷的平均含量为1300~1500μg.g~(-1),与其它湖泊相比,红枫湖、百花湖具有较高的磷负荷。根据Ruttenberg提出的化学连续提取法(SEDEX),可以把沉积物中的磷分为五种形态:(弱)吸附态磷、铁结合态磷、自生磷灰石磷、残留岩屑磷和有机磷。两湖沉积物中以有机磷和铁结合态磷为主,有机磷分别占全磷的60%(红枫湖)和50.3%(百花湖),铁结合态磷为28.25%(红枫湖)和34%(百花湖),这在其它湖泊是极少见的,红枫湖、百花湖沉积物磷具有很高的迁移活性。有机物质是沉积物磷的主要载体,沉积物中-部分有机质被保存下来,其余的矿化降解,同时释放出溶解磷(HPO_4~(2-)),这些溶解磷可以扩散到上覆水体为浮游生物吸收利用,或是以其它形态滞留在沉积物中。沉积物孔隙水中NO_3~-、SO_4~(2-)、Fe~(2+)、Mn~(2+)的剖面分布表明,红枫湖、百花湖沉积物最活跃的有机质降解发生在表层2厘米的沉积物内。根据孔隙水HPO_4~(2-)的浓度梯度,可以计算沉积物-水界面HPO_4~(2-)的交换通量(J_s),红枫湖、百花湖沉积物-水界面磷的扩散通量(J_s)存在明显的季节性变化:在冬春季扩散通量最大,而夏秋季较小,这与传统的认识相反,我们认为这是由于表层沉积物中有机质的矿化降解有关。我们研究了沉积物吸附作用对沉积物磷循环的影响。吸附动力学实验表明,吸附的动力学过程可以用Langmuir或Freundlich方程描述;红枫湖、百花湖沉积物具有很大的理论吸附容量极值(红枫湖的S_m为21.05mgP.g~(-1),百花湖的S_m为15.83mgP.g~(-1));沉积物对磷酸盐的吸附主要是由于其中的未定型的铁氧化物矿物造成的;铁氧化矿物的吸附作用是沉积物中磷滞留的重要机制;经CDB去除铁氧化物处理后,沉积物吸附磷酸根的能力仅为原来的10%。对原状沉积物-界面水柱的释磷实验结果表明:好氧条件下沉积物的溶解磷的释放通量较高,而厌氧条件下相反较低。进一步说明了有机质降解在磷循环中的地位。将沉积物中磷的形态分析数据、孔隙水溶解磷以及吸附盐实验的数据,用于“扩散-平流-反应”模式,结果表明:红枫湖、百花湖沉积物表层有机质(磷)的降解释磷是沉积物-水界面磷交换通量的主要部分,由于沉积物表层易分解有机质的含量较高,铁氧化物的吸附不足以完全阻止沉积物磷酸盐的释放,有机质的氧化降解速率决定了释放通量的大小;而在表层以下的沉积物中铁氧化物的吸附作用是控制孔隙水溶解磷剖面分布的主要因素;红枫湖、百花湖沉积物的整个埋藏历史中(40年),基本没有稳定自生磷灰石矿物的形成。红枫湖、百花湖沉积物全氮平均为沉积物干重的0.36~0.40%,表层含量为0.69~1.06%,沉积物中的含氮化合物主要85%以上是有机氮,沉积物全氮和有机氮呈现表层富集,随沉积深度增加而减少的剖面特征。红枫湖、百花湖沉积物对固定铵氮的能力较强,固定铵的绝对含量分别为434.05 mg.kg~(-1)和(16.94mg.kg~(-1),分别相对于总氮含量的13.53%和12.53%。红枫湖、百花湖水体和沉积物孔隙水中氨态氮(NH_4~+)和硝态氮(NO_3~-)的剖面分布表明:在沉积物-水界面上发生着最剧烈的氮循环作用,这也是清除水体氮负荷的最彻底和唯一的机制。沉积物水界面起到向上覆水体的营养供给和对污染水体自然净化的双重功能。红枫湖、百花湖的沉积物柱芯上有机质剖面通常仅表现“降解阶段”和“堆积阶段”,对红枫湖HF980903-1-2柱芯的分析,发现红枫湖沉积物有机质(碳、氮)的降解代谢过程同样包括类似于洱海沉积物的“沉降-降解-堆积”三个阶段,我们认为是样品的分隔精度不足以反映沉积剖面的细节;同时也说明,红枫湖、百花湖沉积物有机质组成中有较多的“新鲜”、活性的组分,它们的快速降解使得沉积物中有机质不能长期保存。研究表明,经过10年堆积埋藏,沉积物有机质大约有35~76%被降解。上层沉积物中(活性)有机质的迅速分解,是引起沉积物-水界面强烈的营养元素循环的重要原因。剖面对比分析显示,红枫湖、百花湖沉积物有机物质分解过程中,有机碳、磷、氮的改造是不同步的,有机碳相对稳定,而含氮化合物和有机磷则相对易于降解。C_(Org): N_(Org): P_(Org)比值的分析结果表明:红枫湖、百花湖沉积物有机质的来源主要是来源于无纤维素植物。较高的C/N、C/P和较低的N/P,反映了小型湖泊受到较多的人为干扰和流域物质输入影响的特点。
其他摘要One of the main problems in water management is eutrophication. Eutrophication is defined as the enrichment of surface waters with nutrient. Of these nutrients nitrogen (N) and phosphorus (P) are important controlling factors for primary productivity in aquatic ecosystems. Since many years the most common strategy for restoration of these eutrophic surface waters is the reduction of the P Loading, because phosphate is considered to be the natural growth-limiting factor in the most of lakes. The success of the recovery of lakes after reduction of the phosphorus loading however is frequently limited. A major reason is the release of phosphorus from the sediments. Naturally, The biogeochemical processes of nutrients in sediments, especially at the sediment/water interface has been always one of main themes of iimnology. We investigated the vertical profiles of nutrients and chemical species of sediments in two reservoirs-Hongfeng Hu and Baihua Hu in Guizhou to elucidate the biogeochemical characterization of nutrients (P, N, and C) within the early diagenesis. Because the water samples of the two reservoirs had high N: P ratio of between 46:1 to 126:1, phosphorus (P) is considered as the limiting factor for primary productivity in Hongfeng Hu and Baihua Hu. Our studies have shown that sediments of the reservoirs Hongfeng Hu and Baihua Hu had very heavy phosphorus loading, with total-P concentration between 1300 tol500μg. g~(-1). Using the sequential scheme developed by Ruttenberg(1992), we examined forms of solid phosphorus fractions in sediments of the two reservoirs. The dominant P-bearing component in these sediments is organic P (50.3-60%), followed in order of relative dominance by iron-bound P (28.25-34%), authingenic P, adsorbed P, and detrital P. Organic P and iron-bound P vary significantly with depth in the sediment cores. In the two reservoirs the sediment P has strong potential capability to remove out, because organic P and iron-bound P represent the soluble reactive part of sediment P. The organic matter is the principal carrier of P to sediment. A part of the organic material(OM) is buried directly. The other part decomposes, resulting in a release of dissolved HPO_4~(2-) to the pore water. This HPO_4~(-2) either returns to the overlying water and becomes available for uptake by phytoplankton, or is retained in the sediment in an organic or inorganic form. The studies on the chemistry profile of NO_3~-、SO_4~(2-)、 Fe~(2+)、Mn~(2+) in pore water showed that the most obvious derogation of organic matter occurs near the sediment-water interface( within 0-2em) in Hongfeng Hu and Baihua Hu. The flux of HPO_4~(2-) across the interface between water and sediment was calculated based on the concentration gradients of HPO_4~(2-) in pore water and overly water. The research in Hongfeng Hu and Baihua Hu shows that HPO_4~(2-) flux from sediment to water varies seasonally, and was higher in the winter and spring (relative oxidic conditions) than in the summer and autumn (relative anoxic conditions), which is completely different from the traditional and common view. We believe it was mainly contributed to the intensity oxidation decompose of reactive organic matter in surface sediments. The effect of sorption on the sediment-water exchange of HPO_4~(2-) is investigated for sediments of Hongfeng Hu and Baihua Hu. Results of kinetics experiments for dry sediment samples show that the sorption process can be described by the Langmuir or by the Freundlich adsorption isotherm. The data indicate that sorption plays an important role in controlling sediment-water exchange of HPO_4~(2-) in Hongfeng Hu and Baihua Hu(S_m is 21.05mgP.g~(-1), 15.83mgP.g~(-1), respectively). Sorption of HPO_4~(2-) to Fe-oxides and Fe-hydroxide is the most important process responsible for the retention of P in sediment. For example, we found the sorption capacity of the samples removed Fe-oxides and Fe-hydroxide out was 90% less than non-treated samples. The one-dimensional reaction-diffusion model describing pore water HPO_4~(2-) and solid phase P profile were applied for sediment cores of Hongfeng Hu and Baihua Hu. The result shows that the (anoxic/oxic) degradation in surface sediment of organic mater (OM) provides a majority of dissolves HPO_4~(2-) for pore water, which could diffuse upwardly across the sediment-water interface. Due to the OM composed of a lager number of fresh, reactivity species, these OM can degrade very quickly both in oxic or anoxic sediments and release too much dissolve HPO_4~2 to be remove by Fe-oxides sorption. Therefore, within the upper layers of sediment cores, the OM degradation is the key factor to control the cycling of sediment P. With the increasing of depth, bacteria gradually consumed Labile OM. Consequently, the reduction/oxidation of iron mineral will become more and more important to the fate of sediment P. We believe that processes of CFA formation seldom occur during the sedimentary history(only 40 years) of Hongfeng Hu and Baihua Hu. We have examined the distribution of exchangeable, fixed, organic, and total nitrogen in sediments and the concentration ofNO_3~-,NH_4~+ in pore water of Hongfeng Hu and Baihua Hu. The average concentration of total nitrogen is 0.36~0.40% in all sediment cores, and 0.69~1.06% in surface sediment, there are more than 85% organic nitrogen in total nitrogen. The profiles of N_(Org) versus depth and N_(total) Versus depth in sediment cores resemble each other and that of organic carbon concentration versus depth, in which N_(Org), N_(total) are en-rich in surface sediment and decreases gradually with increasing of depth. The sediments of Hongfeng Hu and Baihua Hu have higher ability to fix ammonium in mineral crystal lattice than common soils. The concentrations of "fixed nitrogen" are 434.05 mg.kg~(-1) and 416.94mg.kg~(-1), respectively in sediments of Hongfeng Hu and Baihua Hu. The profiles character of NO_3~- and NH_4~+ in pore water implicate that there are the most impetuous nitrogen cycling in lake system occurring near sediment-water interface, which is effective and unique mechanism sequestering nitrogen load of polluted water. The nitrogen cycling near sediment-water interface not only can supply nutrients to overly water, but also sequester nitrogen load of Eutrophication lakes. The vertical profiles of C_(Org) in most of sediment cores collected from Hongfeng Hu and Baihua Flu suggest a significant characteristic by two stages of "decomposition" and "accumulation", rather than the "three stages" distribution of C_(Org) vertical profile observed in those sediment cores from Erhai Lake. However, the characteristic of the sediment core (HF980903-1-2) resemble those sediment cores from Erhai Lake in vertical profile of C_(Org). There are two reasons why the distribution of C_(Org) vertical profile of sediment cores is different between in the two reservoirs and in Erihai Lake: (1) All sediment cores were segmented into 1 cm intervals, but these slices were not fine to represent some detail stages of vertical profile for most of sediment cores collected from Hongfeng Hu and Baihua Hu. (2) the result, on the other hand, reflected the fact that the organic materials in sediment, especially surface sediments, in Hongfeng Hu and Baihua Hu are more fresh, labile and reactive than that in Erhai Lake. Bacteria will decompose these organic materials so quickly that the OM cannot be preserved in sediment for longer time. Studies show that about 35 ~ 76% sediment OM will be degraded after 10 years burial. The OM degradation in surface sediment was considered as the main sources and mechanism of nutrients regeneration. The result of analysis for atomic ratios C_(Org): N_(Org): P_(Org) indicated that external source of nutrients disturbed the status of nutrients of Hongfeng Hu and Baihua Hu.
页数225
语种中文
文献类型学位论文
条目标识符http://ir.gyig.ac.cn/handle/352002/3562
专题研究生_研究生_学位论文
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王雨春. 贵州红枫湖、百花湖沉积物-水界面营养元素(磷、氮、碳)的生物地球化学作用[D]. 中国科学院地球化学研究所. 中国科学院地球化学研究所,2001.
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