数字高程模型预处理方法的研究进展

数字高程模型(Digital Elevation Model,简称DEM)是地形表面形态属性的数字化表达,被广泛应用于流域水文模拟中河网水系的提取.从DEM直接提取的河网水系及相关的流域地理空间信息,是分布式水文模拟的地理信息平台.由于DEM中洼地和平坦区的存在会影响水流方向的确定和数字河网的正确提取.因此在河网自动提取过程中必须首先对DEM数据进行预处理.本文对国内外各种DEM预处理方法进行了归纳总结.将DEM数据预处理方法分为两大类:分步处理法,以及一体化处理法.分步处理法按处理对象又可分为洼地处理方法和平坦区处理方法两部分;而一体化处理法则采用迭代算法同时对洼地和平地进行处理.     

沉积岩总有机质碳同位素分析的前处理影响

岩石样品中的有机质稳定碳同位素地球化学已经在重建古环境和古植被等领域得到十分广泛的应用。但对样品的前处理方法的系统研究较少。由于岩石样品前处理的方法不同而对有机碳同位素的测量结果所产生的正负偏差,从而导致不能准确地反映样品中所记录的信息。笔者通过大量条件试验,分析了前处理过程中主要影响实验结果的几种因素。①样品粒度的影响：粒度100目的样品可得理想数据,而粒度在60目时两个样品同位素值均相对偏正,200目时灰岩样品也相对偏正;②不同酸浓度的影响：在1～12N浓度酸处理样品其有机质碳同位素没有明显变化,但低等级酸所含杂质明显使数据偏负,加入１５％的氢氟酸对数据没有产生明显影响;③洗除样品中残余酸和烘干温度的影响：为了避免样品中有机质的损失,而不洗除样品中残余的酸,但是样品数据明显偏负并对仪器有损坏,烘干温度100°C时样品部分有机质挥发或升华而使数据相对偏正。     

树木年轮稳定同位素分析样品前处理方法探讨

树木年轮稳定碳氧氢同位素(δ13C、δ18O和δD)作为树轮气候学、树轮生态学研究的一种重要信息,随同位素分析技术的发展得到广泛应用.在利用树轮同位素指标进行古气候、古环境研究中,对原木样品进行纯化得到α-纤维素及硝化纤维是一项耗时、耗力且又必须进行的前处理步骤.总结了目前国内外多种纤维素和硝化纤维提取的实验流程,综述了树轮同位素样品分析制备的提取流程,并提出了本研究组的纤维提取试验流程,讨论了该方法的可行性及存在的问题.建议实验室在利用树轮同位素指标进行古气候和全球变化生态学研究时,应关注树木年轮同位素样品制备流程差异对最终获取的同位素比率的影响,以消除不同实验流程造成的实验结果上的差异,为树轮同位素指标大范围空间指标比较提供基础.     

云南先峰中新世木乃伊化木化石α-纤维素的提取

本文对云南先锋中新世木乃伊化木化石进行α-纤维素实验提取,以验证化石纤维素的可得性。实验利用有机溶剂分离、碱液分离、无机酸分离等方法分别对研究区5件木乃伊化化石样品进行处理,并采用红外光谱检测方法与现代木材α-纤维素和国际标准α-纤维素进行对比试验。实验结果显示,3种提取方法均可以从化石木材中提取出α-纤维素,但过程特征各有不同。其中,有机溶剂分离实验过程耗时最长,碱液分离方法样品损失最大。相比之下,无机酸分离方法对于木乃伊化木化石α-纤维素提取的效率最高。     

不同前处理方法对北方红色风化壳粒度测试影响的初步探讨

选取中国北方岩溶区红色风化壳为研究对象,首先用浓度为30%的H2O2去除样品中的有机质,然后用4种不同的前处理方法分别进行处理,其中方法A未用盐酸溶液处理,方法B、C、D均用盐酸溶液分解可能存在的残余碳酸盐和次生游离氧化物,以消除其对机械颗粒可能存在的胶结作用,此外方法C的HCl在煮沸的条件下反应,方法 B的HCl在常温条件下进行,方法D则更改了超声波振荡的时间。本文样品采用Beckman公司生产的LS13320 型激光衍射粒度测试仪进行测量。结果表明,样品前处理方法对中国北方红色风化壳粒度分析结果有影响,不同的前处理方法使样品的粒度值最大产生5%左右的变化;从实验的稳定性上考虑,4种方法的平行试验标准偏差最大达到6.78%。在现有的认识条件下,粒度测量结果的可重复性是最基本的要求。本文认为方法C的测量效果要好于其他方法。      

100MPa压力下温度和水对干酪根结构状态影响的实验研究

为了实验验证变质沉积物中的碳质物拉曼光谱地质温度计的可用性,利用冷封口式高温高压水热系统将焊封金管内的干酪根于100MPa压力和温度(250-700℃)、有水和无水条件下处理24小时,激光拉曼探针(LRM)分析表明,实验所得碳质物的一级和二级拉曼谱特征(拉曼峰的存在、峰的位置、宽度、高度和面积)随温度系统地变化,所得碳质物的D/O比值随温度升高而减小,但在D/O比-温度关系图上-500℃处有一拐点(极小)。实验条件下处理的干酪根的显微富利叶变换红外谱(micro-FTIR)分析表明,脂族C-H和芳族C-H吸收峰的相对强度在500℃左右急剧变化以及在700℃的实验产物中仍存在含氢的功能团。高温高压条件下,水的存在不利于碳质物的石墨化(有序化)。     

高频红外法测定碳酸盐型石墨矿中固定碳的研究

针对用直接法(或非水滴定法)测定碳酸盐型石墨矿中固定碳时,碳酸盐等杂质分解不完、遇酸分解易飞溅、检测效率低以及用间接法不能准确测定低含量碳酸盐型石墨矿中固定碳的难题,建立用硝酸前处理样品—高频红外吸收法测定碳酸盐型石墨矿中固定碳的方法,并建立校准曲线。从样品的称样量、助溶剂的加入量、酸溶剂及其浓度的选择等方面对该方法进行详细研究。精密度、准确度符合石墨矿中固定碳的分析实验要求,并用国家一级标准物质对其进行了验证(RSD%,n=10)3.37%~0.70%;(RE%,n=10)-1.03%~0.00%。不同检测方法比较发现,本法与直接法、间接法进行比较,具有操作简单、稳定好、快速等特点,提高了石墨矿中固定碳含量的检测效率,适合碳酸盐型石墨矿固定碳的分析测定。     

土壤中总有机碳环境标准样品研制

土壤环境标准样品是土壤生态环境监测质量控制的重要技术工具。目前,土壤中总有机碳环境标准样品仍为中国环境标准样品体系的空缺,特别是配套燃烧氧化-非分散红外法的土壤标准样品一直未曾问世。本文以有机碳含量较高的农用地土壤为原材料,经干燥、研磨、混匀、装瓶、灭菌等加工步骤,制备获得土壤中总有机碳环境标准样品。分层随机抽取10瓶样品进行均匀性检验,经评价统计量F小于临界值F_(0.05)(9,10),瓶间均匀性相对不确定度(u_(bb))为1.5%,样品均匀性良好。在室温避光保存条件下,对样品进行了18个月的稳定性检验,稳定性相对不确定度(u_(lts))为1.2%,样品具有良好稳定性。由中国11家实验室采用燃烧氧化-非分散红外法和重铬酸钾容量法进行协作定值,通过对检测结果的数理统计分析,样品量值评定结果为(25.2±1.4)mg/g。该标准样品为采用燃烧氧化-非分散红外法参与定值的土壤中总有机碳环境标准样品,可作为土壤中总有机碳测定标准方法配套的实物标准,满足土壤生态环境监测及相关研究需求,且与国外同类样品具有可比性。     

鹤庆钻孔沉积物总有机碳、氮含量测定的前处理方法及其环境意义

湖泊沉积物中的总有机碳含量(TOC)、总有机氮含量(TN)和碳氮比值(C/N)已被广泛应用于第四纪湖泊古环境研究中。对湖泊沉积物样品进行TOC和TN测定前, 首先要有效去除沉积物中的无机碳酸盐, 同时较好地保留有机质组分, 才能使实验结果较准确地反映古气候环境的变化。选取鹤庆钻孔不同深度的不同岩性样品, 分别进行粒度、盐酸浓度、洗除残留酸方法等对去除碳酸盐和总有机碳测定结果影响的前处理条件实验, 根据测得的TOC、TN和C/N, 结合总无机碳酸盐含量(TIC), 确定了鹤庆钻孔沉积物有机碳含量测定的前处理方法:室温条件下, 将磨得足够细(无需过筛处理)的样品与足量浓度为2mol/L盐酸充分反应24小时, 期间超声震荡3次, 采用离心加速沉淀的方法清洗酸处理样品至中性, 烘干, 研磨均匀上机测定。结果显示, 该流程可有效去除沉积物中的无机碳酸盐, 测得的TOC、TN数值具有很好的稳定性和可重复性。在此基础上测定了鹤庆钻孔沉积物样品的TOC、C/N和TIC, 它们间存在很好的正相关关系, 指示了西南季风强度的变化。      

饱和烃经5分子筛络合前后单体烃碳同位素分析对比研究

通过对自配标准样品(正构烷烃)进行5分子筛吸附试验,测定了用5分子筛吸附法分离前后正构烷烃、异构烷烃和环烷烃碳同位素值,探讨试验前后碳同位素值的变化。尽管实验过程中样品经过85℃长时间加热回流及吸附样品的5分子筛用氢氟酸酸化处理,但实验结果经仪器检测,证明该方法对正构烷烃碳同位素值影响因素不大。本文还介绍了原油和煤可溶有机质中饱和烃络合前后的单体烃碳同位素分析方法。并在前人工作的基础上,改进采用微型索氏抽提加热回流实验装置,既提高了样品的回收率,也减少了样品中轻组分的损失。     

Determination of the aromaticity and the degree of aromatic condensation of a thermosequence of wood charcoal using NMR

Quantifying the role of black carbon (BC) in geochemical processes is difficult due to the heterogeneous character of its chemical structure. Chestnut wood charcoal samples produced at heat treatment temperatures (HTT) from 200-1000 °C were analysed using two different solid state ¹³C NMR techniques. First, aromaticity was determined as the percentage of total signal present in the aromatic region of ¹³C direct polarisation (DP) spectra. This was found to increase through the low temperature range of 200-400 °C; at higher temperatures, aromaticity was found to be >90%. Second, aromatic condensation was determined through the measurement of the chemical shift of ¹³C_benzene sorbed to the charcoals, which is influenced by the presence of “ring currents” in the aromatic domains of the charcoals. This technique was less sensitive to molecular changes through the lower temperature range, but showed there was a smooth increase in the degree of condensation of the aromatic structures with increasing temperature through the temperature range 400-1000 °C. Ab initio molecular modelling was used to estimate the size of aromatic domains in the charcoals based on the strength of the ring currents detected. These calculations indicated that charcoals produced at temperatures below 500 °C contain aromatic domains no larger than coronene (7 ring). At higher temperatures the size of these domains rapidly increases, with structures larger than a 19 ring symmetrical PAH being predominant in charcoals produced at temperatures above 700 °C. Data from this study were found to be generally consistent with previously published measurements using the benzenepolycarboxylic acid (BPCA) molecular marker method on the same set of samples.     

Microbial mineralization and assimilation of black carbon: Dependency on degree of thermal alteration

Black carbon is degraded slowly in the environment and its formation can therefore be an effective sink for atmospheric CO₂. This study examined whether charcoal is assimilated by microorganisms or not and estimated the rate of mineralization depending on the degree of thermal alteration of the black carbon. Charcoals were produced at three different temperatures from homogeneously ¹⁴C labelled plant material and incubated in soil, and ¹⁴C in the evolved CO₂ and the microbial biomass was measured. Unlike parallel plant samples, CO₂ evolution from the charcoals showed no lag phase, but a period of faster CO₂ evolution for the first 5–8 days followed by a period of slow evolution. The mineralization of charcoal appeared to decrease with increasing temperature at which it was produced. This was also the case after the initial period of fast CO₂ evolution. With the techniques used, it was not possible to observe any microbial assimilation of charcoal, either because it did not occur, or because the methods used were not sufficiently sensitive. However, the lack of a lag phase in the CO₂ evolution from the charcoals is in line with earlier evidence that charcoal is initially oxidized at the surfaces by abiotic processes.     

现代植物炭屑形态的初步分析及其古环境意义*

通过对23种现代植物炭屑的观察、测量以及对草本、木本炭屑模拟破碎试验后的测量统计发现:现代植物炭屑形态根据其长宽比(L/W)和形态特征可以分为3个类型:1)草本型炭屑,L/W最大,平均为10.2±1.3, 呈长-薄条型、针型、簇纤维型,边缘及断口截然,棱角分明,有些具有气孔构造,很少有不规则的形态出现; 2)木本型炭屑(灌木+乔木),L/W较小,平均3.1±0.2,多呈方~长方型或立方体型,边缘多参差不齐,有些横向断口有粗大木纤维露出,相对致密; 3)阔叶类植物叶片炭屑,L/W最小,平均1.7±0.1,薄片状、网状,絮状,易碎。进一步通过对6个典型草原和森林表土样品的实验室分析,发现现代土壤中的炭屑颗粒大小相对现代植物炭屑颗粒大小总体有所减小,但草原土壤中炭屑长宽比相对森林土壤炭屑仍然较大,土壤中炭屑形态和部分结构鉴别特征仍能保留。表明L/W值与炭屑结构特征可以用来区分多数草本与木本植物炭屑。在此基础上,通过对黄土高原渭南剖面S₁以来不同层位12个地层样品的炭屑形态分析,初步研究了不同草本、木本植物炭屑形态变化的特点和环境意义。     

Comparison of gas with liquid chromatography for the determination of benzenepolycarboxylic acids as molecular tracers of black carbon

Existing methods for black carbon (BC) quantification measure different parts of the BC continuum, which complicates the calculation of a global BC budget. Benzenepolycarboxylic acids (BPCA) are used as molecular markers to quantify and characterize BC in soils and sediments using gas chromatography for BPCA separation (GC-BPCA). Recently, this method was refined for BC analysis in seawater using high performance liquid chromatography (LC-BPCA), which omits the cleaning steps and derivatization necessary in GC analysis. As yet it is not clear whether the two analytical methods yield similar results. Here we apply both methods to a suite of laboratory produced charcoals derived from wood and grass. We found systematically lower total BPCA-C contents and larger analytical variability for all tested charcoals when using GC-BPCA compared to LC-BPCA, the latter giving 1.5 ± 0.3 times higher yields for the charcoal samples formed at 275-700 °C. At lower and higher pyrolysis temperatures the differences between the two analytical methods were larger. The main reason for the differences between the two methods is the loss of BPCA during sample preparation for GC analysis. We propose a correction factor of 1.5 to account for at least part of these losses. No qualitative biases, i.e. towards more or less functionalized BPCAs, were observed between the two methods. The relative contribution of mellitic acid C to total BPCA-C, a measure for the degree of condensation of BC, was the same in the two analytical techniques. Qualitative differences between wood and grass charcoals as detected by both methods were small.     

Variability in oxidative degradation of charcoal: Influence of production conditions and environmental exposure

Charcoal is a key component of the Black Carbon (BC) continuum, where BC is characterized as a recalcitrant, fire-derived, polyaromatic material. Charcoal is an important source of palaeoenvironmental data, and of great interest as a potential carbon sink, due to its high apparent environmental stability. However, at least some forms of charcoal are clearly susceptible to environmental alteration and degradation over relatively short timescales. Although these processes have importance for the role of charcoal in global biogeochemistry, they remain poorly understood.Here we present results of an investigation into the susceptibility of a range of charcoal samples to oxidative degradation in acidified potassium dichromate. The study examines both freshly-produced charcoal, and charcoal exposed to environmental conditions for up to 50,000 years. We compare the proportion of carbon present in different forms between the samples, specifically with respect to the relative chemical resistance of these forms. This was undertaken in order to improve understanding of the post-depositional diagenetic changes affecting charcoal within environmental deposits.A wide range in chemical compositions are apparent both within and between the sample groups. In freshly-produced charcoal, material produced at 300 °C contains carbon with more labile forms than charcoal produced at ?400 °C, signifying a key chemical change over the 300-400 °C temperature range. Charcoal exposed to environmental depositional conditions is frequently composed of a highly carboxylated aromatic structure and contains a range of carbon fractions of varying oxidative resistance. These findings suggest that a significant number of the environmental charcoals have undergone post-depositional diagenetic alteration. Further, the data highlight the potential for the use of controlled progressive oxidative degradation as a method to characterize chemical differences between individual charcoal samples.     

The transformation and mobility of charcoal in a fire-impacted watershed

The incomplete combustion of fossil fuels and biomass has resulted in the global-scale distribution and accumulation of black carbon (BC) in the environment. Recently, the molecular identity of BC in the dissolved phase has been distinguished from that of natural organic matter. However, many of the processes that control BC cycling remain unidentified. We investigate changes in soil charcoal particle morphology and chemical composition using surface area analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, chemical oxidation, and ¹³C NMR spectroscopy. A comparison of soil charcoals differing in age by 100 years shows that aged charcoal has lower specific surface areas, higher BC/OC ratios, direct associations with soil minerals and microbial biomass, and a greater abundance of non-aromatic carbon. The water-soluble portion of soil charcoal and dissolved organic matter (DOM) from the watershed were also characterized by electrospray ionization mass spectrometry. Aqueous charcoal extracts are comprised mostly of condensed aromatic ring structures (CARS) which are also present in soil pore, river, and ground water samples. We present indirect evidence and a chemical rationale for a microbial BC dissolution mechanism. Furthermore, the speciation of CARS in the soil solution versus river and ground water provides molecular evidence of reactivity in the dissolved phase. The dissolution and export of soil BC are presently unmeasured fluxes with important implications for the global carbon cycle.     

Quantitative C NMR of whole and fractionated Iowa Mollisols for assessment of organic matter composition

Both the concentrations and the stocks of soil organic carbon vary across the landscape. Do the amounts of recalcitrant components of soil organic matter (SOM) vary with landscape position? To address this question, we studied four Mollisols in central Iowa, two developed in till and two developed in loess. Two of the soils were well drained and two were poorly drained. We collected surface-horizon samples and studied organic matter in the particulate organic matter (POM) fraction, the clay fractions, and the whole, unfractionated samples. We treated the soil samples with 5 M HF at ambient temperature or at 60 °C for 30 min to concentrate the SOM. To assess the composition of the SOM, we used solid-state nuclear magnetic resonance (NMR) spectroscopy, in particular, quantitative ¹³C DP/MAS (direct-polarization/magic-angle spinning), with and without recoupled dipolar dephasing. Spin counting by correlation of the integral NMR intensity with the C concentration by elemental analysis showed that NMR was ?85% quantitative for the majority of the samples studied. For untreated whole-soil samples with <2.5 wt.% C, which is considerably less than in most previous quantitative NMR analyses of SOM, useful spectra that reflected ?65% of all C were obtained. The NMR analyses allowed us to conclude (1) that the HF treatment (with or without heat) had low impact on the organic C composition in the samples, except for protonating carboxylate anions to carboxylic acids, (2) that most organic C was observable by NMR even in untreated soil materials, (3) that esters were likely to compose only a minor fraction of SOM in these Mollisols, and (4) that the aromatic components of SOM were enriched to ∼53% in the poorly drained soils, compared with ∼48% in the well drained soils; in plant tissue and particulate organic matter (POM) the aromaticities were ∼18% and ∼32%, respectively. Nonpolar, nonprotonated aromatic C, interpreted as a proxy for charcoal C, dominated the aromatic C in all soil samples, composing 69-78% of aromatic C and 27-36% of total organic C in the whole-soil and clay-fraction samples.     

Premières datations directes de défrichements protohistoriques sur les chaumes secondaires des Vosges (Rossberg,Haut-Rhin). Approche pédoanthracologique

The age of the upland grasslands of the Vosges Mountains is still not well known. On the basis of the study of historical archives, it was assumed that the forest clearings, which led to grasslands establishment, were done by the monks who colonized the Vosges valleys between the 7th and the 8th centuries. Our pedo-anthracological study raises questions about this hypothesis, based on the discovery of Juniperus communis charcoal in soils from the 2nd or 1st century BC. This plant specie is characteristic of grasslands developing into fallows. The occurrence of Juniperus communis charcoals indicates that upland grasslands did exist at least 800 years earlier than it was expected before our study, i.e. at least since the late Iron Age. To cite this article: D. Schwartz et al., C. R. Geoscience 337 (2005).     

Comparing fire-history interpretations based on area, number and estimated volume of macroscopic charcoal in lake sediments

Sedimentary charcoal particles from lakes are commonly used to investigate fire history. Fire-history reconstructions are based on measuring the surface area or counting the number of charcoal fragments in adjacent samples. Recently, the volume of charcoal particles was advised as a more accurate method for quantifying past charcoal production. Large charcoal datasets, used to synthesize global fire history, include these different types of charcoal measurements and implicitly assume that they provide comparable fire-history information. However, no study has demonstrated that this assumption is valid. Here we compare fire-frequency reconstructions based on measurements of charcoal area and number, and estimates of charcoal volume from two lake sediment records from the eastern Canadian boreal forest. Results indicate that the three proxies provide comparable fire-history interpretations when using a locally defined threshold to identify fire events.     

微炭屑的几种统计方法比较及其对人类活动的指示意义

微炭屑是研究火的历史和过去人类活动、重建古生态的一项重要指标。它一般指长轴小于120μm、黑色不透明的炭化颗粒。常用点接触法（11刻点和202刻点）、图像识别法、颗粒计数法和分粒级法进行微炭屑统计。本文利用不同方法求得的微炭屑面积浓度或颗粒浓度曲线显著相关,相关系数在0.6以上（p<0.05）,表明这几种方法的微炭屑统计结果具有相似的变化趋势,尤其是两种点接触法与图像识别法的统计结果更加相近,相关系数分别为0.79与0.88;  颗粒计数法与点接触法、图像识别法的相关系数是0.75和0.74。分粒级法与点接触法、图像识别法和颗粒计数法的相关性随着粒级的变化而不同。两种点接触法的微炭屑统计结果的相关系数高达0.93,反映了这两种方法所得微炭屑统计结果具有几乎相同的变化趋势。202刻点接触法由于与其他统计法的相关性都比较高,统计视域多且鉴定统计速度快,是进行微炭屑统计的最佳方法。微炭屑浓度高的时段出现在繁荣的文化期,可能指示着强烈的人类活动。