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典型地区海鸟粪土沉积层中色素和甲基汞分析及生态环境意义
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摘要
气候环境变化是当前全球变化研究高度关注的焦点,是21世纪人类发展面临的重大课题。与人类文明发展密切相关的晚全新世气候变化是过去全球变化(PAGES)计划项目的核心内容,对于这一时期气候变化的深入研究可以更好的理解气候变化的规律、特征和机制,为气候变化研究提供自然变化背景值,从而更好的理解人类活动对气候的影响程度,有利于对当前和未来气候变化的评估和预测。学者们在不同的时间和空间层次上对自然界中保存着丰富环境信息的记录载体进行了大量的研究。其中,南极和南海西沙群岛由于其特殊的地理位置和气候条件,对气候变化和人类活动的变化响应灵敏,是研究过去全球变化包括古气候、古生态、古环境的理想区域。本文在时间尺度上选取与人类生存环境密切相关的晚全新世,空间上选取高纬度的东南极地区典型的企鹅粪土沉积层和低纬度地区的中国南海西沙群岛典型的海鸟粪土沉积进行分析研究。应用多学科交叉的研究方法,通过有机生物标志物,结合其它生物地球化学指标,探讨典型区域气候与生态系统的变化过程,分析海鸟生物传输对生态系统的影响。涉及的主要内容及研究结果如下:
     1.沉积色素分析方法对比研究
     沉积色素分析方法种类繁多,建立了沉积色素的高效液相色谱分析和液质联用分析方法。离子对缓冲溶液有效地提高了高效液相色谱法对叶绿素a和伪枝藻色素的分离效果和灵敏度,相对标准偏差均在10%以内。液质联用法采用乙腈体系,同时加入少量甲酸,明显提高了离子化效率和灵敏度,色素的分离效果、丰度和稳定性均较好。另外,将高效液相色谱法和液质联用法同其它沉积色素分析法,包括传统的分光光度法和近红外光谱法的分析效果进行对比,不同分析方法的效果存在较大的差异,液质联用法显示了巨大的优势。近红外光谱法,操作最为简便快捷,但只局限于估算样品中叶绿素a的含量。紫外可见分光光度法仪器设备和操作都比较简单、成本低且分析速度快,但是分析精度不够高,特异性较差。高效液相色谱法的分析精度和特异性均较高,但是色谱条件要求更高,在技术上存在很多困难和挑战。液质联用法的分析精度、灵敏度和特异性非常高,对目标化合物的分离程度要求不高,具有高的灵敏度和特异性,操作简单,可控性强。
     2.过去800年东南极罗斯海地区的紫外辐射历史的沉积色素记录
     对东南极罗斯海地区沉积样品中的沉积色素进行了分析,并结合其它地球化学指标重建了东南极罗斯海地区过去800年来的紫外辐射记录和整体光强度的变化历史。结果表明,过去800年来东南极罗斯海地区至少经历了四次明显的紫外辐射高峰期,而且从历史记录来看现代的紫外辐射强度应最高。影响到达湖泊的紫外辐射强度的因素繁多,罗斯海地区在190-320aBP时期,紫外辐射与整体光强度变化趋势一致,对应于气候恶劣的小冰期,表明紫外辐射强度的变化与第一类因子有关,如湖泊DOC、冰雪覆盖程度、天气条件等;其它时期紫外辐射与整体光强度没有明显的相关性,表明紫外辐射的变化主要归因于臭氧变化和太阳光谱变化。从历史角度来看紫外辐射强度与太阳活动呈现出一定的反相关关系,太阳活动弱的时期,对应的紫外辐射相对较强,但该自然过程随着近现代人类活动的干扰有可能发生显著变化。
     3.东南极湖泊沉积物生产力和物质成分的近红外光谱快速分析
     对东南极罗斯岛粪土沉积柱以及莫愁湖MC2沉积剖面进行了近红外光谱分析,利用近红外光谱数据重建了东南极湖泊生产力的变化历史,恢复了沉积剖面中各物质组成的相对比例,建立了元素含量与光谱指标间的统计关系模型。结果显示,罗斯岛沉积剖面样品中的叶绿素a含量与近红外反射光谱在650-700nm处的谷面积表现出明显的线性相关关系,利用数学建模可以预测样品中叶绿素a的含量,指示湖泊生产力变化历史;但是预测叶绿素a与实测的绝对含量存在一定差异,该方法只可以作为一种快速的半定量的预测湖泊生产力的方法。莫愁湖样品的近红外光谱数据主成分(PCA)分析结果表明,PCA分析主因子1载荷值与指示生产力变化的有机质热解烃类化合物S2指标高度相关,比谷面积法更好,能够更准确的反映湖泊生产力的变化。同时,结合纯鸟粪、纯藻类与土壤样品的光谱曲线,利用端源分解的方法,成功计算得到了罗斯岛四个沉积剖面中各物质来源所占的比例。通过主成分回归(PCA)和偏最小二乘法(PLS)两种模型,建立多种元素含量与不同光谱指标间的统计关系模型,且PLS模型所预测的数据精确度要比PCR高,可用于样品化学元素含量的预测。
     4.基于色素的东南极湖泊浮游藻类分类方法的研究
     基于高效液相色谱-质谱联用方法(HPLC-APCI-MS)测定了东南极罗斯海地区沉积样品中色素的含量,运用藻类色素化学分类软件CHEMTAX恢复了东南极罗斯海地区湖泊藻类种群结构变化历史,并探讨了南极海鸟生物传输对湖泊藻类种群结构的影响。结果表明,东南极罗斯海地区的湖泊中分布着蓝藻、绿藻、硅藻、隐藻和甲藻等多个门类,其中,绿藻、硅藻和蓝藻为优势种群。海鸟生物传输带来的营养物质促进了湖泊中藻类种群的发展,提高了湖泊初级生产力水平。受到海鸟活动影响较大的BI和MB6沉积剖面中叶绿素a和叶绿素b存在明显的正相关关系,主要以绿藻为主,丰度明显高于其它种群,表明鸟粪输入在促进湖泊藻类生物量增加的同时尤其促进了绿藻的生长。在BI和MB6剖面中,绿藻和硅藻与甲藻丰度表现为相反的关系,同时CL2剖面中蓝藻和甲藻丰度呈反相关,表明企鹅粪输入的营养成分可能会导致湖泊中不同藻类生长出现竞争,相对丰度发生变化,从而导致湖泊生态群落结构发生改变。基于沉积色素的化学分类法CHEMTAX虽然存在一定的不足,但总的来说,还是能够比较准确的表征出研究区域内的藻类优势种群和丰度相对变化,在南极湖泊生态群落结构演化历史研究中具有潜在的应用性。
     5.鸟生物传输对西沙群岛生态系统甲基汞污染物的影响
     通过实验建立了微波萃取-原子荧光光谱法测定海鸟生物粪样品中的甲基汞方法,并利用此方法对中国南海西沙群岛广金岛和晋卿岛上的古鸟粪和现代鸟粪样品及粪土沉积剖面样品进行了甲基汞分析,探讨了海鸟生物传输对偏远的西沙群岛生态系统中甲基汞污染物的影响。结果表明,西沙群岛古鸟粪和新鲜鸟粪中的甲基汞、总汞和甲基汞在总汞中的百分比含量都很高,说明排便是海鸟吸收和排泄甲基汞的一个过程,在海鸟体内的甲基汞循环中起着重要的作用。甲基汞和P元素的正相关关系表明鸟粪的输入控制着工业革命之前的粪土沉积层中甲基汞的含量,但是近年来人类活动带来的汞污染严重影响了工业革命之后粪土沉积层中甲基汞的分布,海鸟通过生物放大和生物传输作用影响粪土沉积层中的甲基汞水平。粪土沉积样品和古鸟粪样品中的甲基汞百分比含量高达20%左右,而且年龄较老的古鸟粪和粪土沉积样品中的甲基汞比例高于年轻样品中的含量,同时样品中微生物活动较弱,表明粪土沉积物中甲基汞百分比的变化主要受控于海鸟粪便的输入。海鸟生物传输不仅为西沙群岛生态系统发育带来了必需的营养物质,同时也为偏远的岛屿生态环境带来了大量的污染物,有可能威胁岛上居民的身体健康。
Climate change is a focus of global change research. It is an important issue to human development in the21st century. Late Holocene climate change is the central part of Past Global Changes (PAGES), which is closely related to the evolution of human civilization. Knowledge on the history of climate change in this period can provide us a perspective for understanding and predicting future global climate changes. A number of studies in paleoclimate-environment research at different temporal and spatial scales have been carried out. Since the special geographical and climate conditions, Antarctica and Xisha Islands of South China Sea are sensitive to global climate change and are the ideal research areas for the reconstruction of paleoenvironment. In the present dissertation, we focus on the Late Holocene which is closely related to human activities, and choose several sediment sequences with seabird relics and some environmental media samples (including soil, rock, guano and plant) collected from Antarctica and Xisha Island of South China Sea, respectively. Using multi-disciplinary research method combined with other bio-geochemical indicators to explore the influence of seabird biotransmission on remote ecosystems. Main conclusions of this paper are outlines as follows:
     1. Comparative study on the analysis method of deposited pigment
     There are many different kinds of methods for deposited pigment analysis. We established HPLC and HPLC-MS method for pigment analysis in lake sediments. HPLC method improves the separation effect of Chlorophyll a and Scytonemin significantly, using methanol and acetone elution solvent with some ion pair buffer solution with a relative standard deviations within10%. HPLC-MS method uses acetonitrile with a small amount of formic acid as elution solvent to improve the ionization efficiency and sensitivity. This method shows fine separation effect, abundance and the stability. Compared with other methods, including UV-Vis spectrophotometry and near-infrared reflectance spectroscopy (NIRS), HPLC-MS is proved to be superior. Although different methods have shown a relatively reliable analysis results, there are still some differences in analysis method and effects. NIRS just can be used as an indirect method for rapid assessment of chlorophyll a content. The equipment and operation of UV-Vis spectrophotometry is relatively simple and timesaving, but the accuracy is not high enough, and the specificity is relatively poor. The HPLC method demands strict chromatography conditions, and it is very difficult to separate all the pigments by HPLC. The requirement of separation effect by HPLC-MS is not so rigour, and HPLC-MS is more sensitive, rapid and accurate compared with other traditional methods.
     2.800-year UVR record of the Ross Sea area, East Antarctica
     We used high performance liquid chromatography (HPLC) combined with mass spectrometry (MS) to analyze deposited pigments (including chlorophyll a, chlorophyll b, canthaxanthin, echinenone, zeaxanthin, scytonemin and mycosporine-like amino acids) in two sediment cores collected from the Ross Sea area, East Antarctica. We explored the sources and characteristics of each pigment, reconstructed an800-year record of ultraviolet radiation (UVR) and total incoming light intensity (UVR+PAR (photosynthetic active radiation)), and assessed the possible factors that have influenced UVR changes in this region. The results indicated at least four UVR peaks during the past800years, corresponding to0-50a BP,250-320a BP,350-450a BP and520-610a BP, with the intensity from the most recent sediments being the highest. A comparison of two proxies for UVR and UVR+PAR indicated a similar pattern between190and320a BP, suggesting that factors controlling the UVR intensity in the Ross Sea area may be related to changes in insolation during the Little Ice Age. Both of these proxies are, however, weakly correlated during other periods and the reconstructed UVR and solar activity records indicate some negative correlation. Historically, the inverse correlation between these two parameters may be a natural process, but during the modern period, this process was strongly affected by anthropogenic activities.
     3. The application of near infrared reflectance spectroscopy in the reconstruction of lake primary productivity in East Antarctic area
     The near infrared reflectance spectroscopy (NIRS) was determined in five sediment profiles collected from East Antarctica, and the potential application of NIRS in reconstructing historical changes of Antarctic lake primary productivity was studied. Meanwhile, we explored the environmental implications of spectral data using statistical analysis method. The results showed that the appearance of trough at650-700nm is an important marker for distinguishing the sedimentary organic matter source from between guano and algae. The measured chlorophyll a content had significantly positive correlations with the trough area between650-700nm, and no distinct trough was found in the sediments with organic matter completely derived from guano. Modeling results showed that the spectro-inferred chlorophyll a content and the measured data have consistent change trends versus depth, and thus the dimensionless trough area could be used as an independent proxy for rapidly reconstruction for the historical fluctuation of Antarctic lake primary production. The principal component analysis (PCA) of MC2sediment profile showed that the factor loadings of PCA displayed similar change pattern with S2index, a reliable proxy for the change in historical lake primary productivity. Compared with trough area method, PCA statistical approach was more accurate. Combined with the spectrum of environmental media (soil, guano and algae), we explored the proportion of each substance (soil, guano and algae) in the bulk sample and established statistical models between chemical element content and spectral indices using PCA and PLS (Partial Least Squares) methods.
     4. The application of sediment pigment in the reconstruction of algae community structure in East Antarctica lakes
     Deposited pigments were analyzed using high performance liquid chromatography (HPLC) combined with mass spectrometry (MS) on three sediment cores from the Ross Sea area, East Antarctica. Based on the CHEMTAX analyses, we reconstructed the record of algae community in East Antarctica lakes and examined the effects of seabird activity on lake primary productivity and algae community structure. The results showed that there were several algae classes in the study area, including cyanophyta, cryptophyta, chlorophyta, diatom and pyrrophyta, where chlorophyta, cyanophyta and diatom were the dominant classes. The positive correlation between chlorophyll a and P concentration indicated that the input of seabird droppings promote the growth of algae and improve lake primary productivity. Chlorophyta is the main species in BI and MB6profiles, and its abundance is significantly higher than the others. Combined with other geochemical indicators, we found that the influence of seabird activity in BI and MB6profiles was higher than CL2core. Higher nutrient content enhances algae biomass, in particular, promotes the growth of chlorophyta. The remarkable positive correlation between chlorophyll a and chlorophyll b (r=0.86, n=40and r=0.84, n=29) in BI and MB6cores further confirmed that.chlorophyta is the dominant species. The input of seabird droppings can cause competition of algae in lakes, leading to the change of community structure. Although there are certain deficiencies in CHEMTAX program, it can be a relatively more accurate in characterizing the abundance of dominant alage species in the study area, and is currently one of the most widely used methods.
     5. The impact of Seabird biotransmission on methylmercury distribution in Xisha Island ecosystem
     We established the analytical method for the determination of methylmercury in seabird excrement and ornithogenic sediment samples using atomic fluorescence spectroscopy coupled with microwave-assisted extraction. Using this method, we determined the distribution and main source of methylmercury in ornithogenic coral sand sediments and pure guano collected from Guangjin and Jinqing islets of the South China Sea and explored the impact of seabird biotransmission on remote Xisha Island ecosystem. Results showed that the levels of MeHg, total Hg (THg) and the proportions of MeHg in THg (%MeHg) are very high in both fresh and ancient guano samples.%MeHg in ancient guano exceeded70%, much higher than that in fresh seabird droppings (-45%). These results suggest that excreting feces likely plays an important role in the cycling of MeHg in seabirds. MeHg concentration has significant positive correlations with THg and TOC, suggesting that MeHg in the ornithogenic sediments probably shares a common source with THg and TOC. The correlation between MeHg and P indicates that guano input is the dominant factor controlling the concentration of MeHg before the Industrial Revolution, but the emission of modern Hg pollutants derived from human activities might have significant effects on post-industrial MeHg distribution in seabird droppings and ornithogenic sediments through biomagnification and biotransport.%MeHg in the ornithogenic coral sand sediments is extremely high, ranging from10%-30%with an average of~20%. Furthermore, older guano and ornithogenic sediment samples generally have a larger proportion of MeHg in THg. Combined with lack of influence from microbial activity, guano was identified as the major source of MeHg in the ornithogenic coral sand sediments in the Xisha Islands. Though the input of seabird-derived nutrients promote the development of coral island ecosystem, it also transports a lot of pollutants into remote island ecosystem, threating the health of residents on the island.
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