Independent measurement of biogenic silica in sediments by FTIR spectroscopy and PLS regression

We present an independent calibration model for the determination of biogenic silica (BSi) in sediments, developed from analysis of synthetic sediment mixtures and application of Fourier transform infrared spectroscopy (FTIRS) and partial least squares regression (PLSR) modeling. In contrast to current FTIRS applications for quantifying BSi, this new calibration is independent from conventional wet-chemical techniques and their associated measurement uncertainties. This approach also removes the need for developing internal calibrations between the two methods for individual sediments records. For the independent calibration, we produced six series of different synthetic sediment mixtures using two purified diatom extracts, with one extract mixed with quartz sand, calcite, 60/40 quartz/calcite and two different natural sediments, and a second extract mixed with one of the natural sediments. A total of 306 samples—51 samples per series—yielded BSi contents ranging from 0 to 100 %. The resulting PLSR calibration model between the FTIR spectral information and the defined BSi concentration of the synthetic sediment mixtures exhibits a strong cross-validated correlation ( \( {\text{R}}^{ 2}_{\text{cv}} \)  = 0.97) and a low root-mean square error of cross-validation (RMSECV = 4.7 %). Application of the independent calibration to natural lacustrine and marine sediments yields robust BSi reconstructions. At present, the synthetic mixtures do not include the variation in organic matter that occurs in natural samples, which may explain the somewhat lower prediction accuracy of the calibration model for organic-rich samples.     

Fourier transform infrared spectroscopy,a new method for rapid determination of total organic and inorganic carbon and biogenic silica concentration in lake sediments

We demonstrate the use of Fourier transform infrared spectroscopy (FTIRS) to make quantitative measures of total organic carbon (TOC), total inorganic carbon (TIC) and biogenic silica (BSi) concentrations in sediment. FTIRS is a fast and cost-effective technique and only small sediment samples are needed (0.01 g). Statistically significant models were developed using sediment samples from northern Sweden and were applied to sediment records from Sweden, northeast Siberia and Macedonia. The correlation between FTIRS-inferred values and amounts of biogeochemical constituents assessed conventionally varied between r = 0.84–0.99 for TOC, r = 0.85–0.99 for TIC, and r = 0.68–0.94 for BSi. Because FTIR spectra contain information on a large number of both inorganic and organic components, there is great potential for FTIRS to become an important tool in paleolimnology.     

A brief introduction to recent applications of several sediment-analysis techniques in palaeolimnological studies-dry bulk density and water content, mineral magnetism, carbonate content, and content of total organic carbon, nitrogen content and c

ChalacteriStics of lacustrine sediments are often capable of ~ring the hydrological regales of the lakeand its environment and human achvihes in itS catclunent during the sedimentahon of these sedimentS.Therefore, by identifying these characteristics of sedimentS, it is likely to postUlate the physicalconditions in and around the lake during geological periods. Such reconstrUction of palaeoenvironmentshas become an increasingly important branch of ear sciences as there has been an expanded n…     

Climate-related cyclic deposition of carbonate and organic matter in Holocene lacustrine sediment,Lower Michigan,USA

Records from lake sediment cores are critical for assessing the relative stability of climate and ecosystems over the Holocene. Duck Lake in south-central Lower Michigan, USA, was the focus of a study that identified how changes in the geochemical variables in lake sediments relate to variations in regional climate and local land use during the Holocene. More than 8.5 m of lacustrine sediment were recovered using Livingston and freeze corers and analyzed for organic carbon, inorganic (carbonate) carbon, total nitrogen, and trace metals. Repeating packages of sediment (1–10 cm thick) that grade from light (inorganic carbon-rich) to dark (organic carbon-rich) were found from the surface to a depth of about 8 m. Variations in the high-resolution gray scale data from core X-radiographs are highly correlated to the relative amount of inorganic carbon. Geochemical analyses of the upper 8.5 m of sediment revealed a wide range of values: 0.05–10.6% for inorganic carbon (i.e. 0.5–89% calcium carbonate) and 1.1–28% for organic carbon (i.e. 2.7–70% organic matter). Organic carbon to nitrogen ratios indicate that most of the sediment organic matter is produced within the lake. A core chronology based on eight AMS radiocarbon dates shows low sediment accumulation rates (0.05 cm/year) from 10,000 to 3,800 cal year BP and higher sediment accumulation rates (0.1–0.3 cm/year) from 3,800 cal year BP to present. We suggest that carbonate accumulates during relatively dry times, whereas organic matter accumulation dominates when nutrient input to the lake is enhanced by wetter climate. The Duck Lake core records a distinct low point in inorganic carbon deposition that may be related to the 8.2 ka cooling event now documented from several sites in North America. Spectral analysis of gray scale values shows significant ~200-year periodicities over the past 8,000 years, hypothesized to result from climate changes induced by solar forcing. Concentrations of trace metals (e.g. lead, iron, copper, zinc) indicate the onset of regional anthropogenic influence about 150 cal year BP.     

Loss on ignition as a method for estimating organic and carbonate content in sediments: reproducibility and comparability of results

Five test runs were performed to assess possible bias when performing the loss on ignition (LOI) method to estimate organic matter and carbonate content of lake sediments. An accurate and stable weight loss was achieved after 2 h of burning pure CaCO₃ at 950 °C, whereas LOI of pure graphite at 530 °C showed a direct relation to sample size and exposure time, with only 40-70% of the possible weight loss reached after 2 h of exposure and smaller samples losing weight faster than larger ones. Experiments with a standardised lake sediment revealed a strong initial weight loss at 550 °C, but samples continued to lose weight at a slow rate at exposure of up to 64 h, which was likely the effect of loss of volatile salts, structural water of clay minerals or metal oxides, or of inorganic carbon after the initial burning of organic matter. A further test-run revealed that at 550 °C samples in the centre of the furnace lost more weight than marginal samples. At 950 °C this pattern was still apparent but the differences became negligible. Again, LOI was dependent on sample size.An analytical LOI quality control experiment including ten different laboratories was carried out using each laboratory's own LOI procedure as well as a standardised LOI procedure to analyse three different sediments. The range of LOI values between laboratories measured at 550 °C was generally larger when each laboratory used its own method than when using the standard method. This was similar for 950 °C, although the range of values tended to be smaller. The within-laboratory range of LOI measurements for a given sediment was generally small. Comparisons of the results of the individual and the standardised method suggest that there is a laboratory-specific pattern in the results, probably due to differences in laboratory equipment and/or handling that could not be eliminated by standardising the LOI procedure.Factors such as sample size, exposure time, position of samples in the furnace and the laboratory measuring affected LOI results, with LOI at 550 °C being more susceptible to these factors than LOI at 950 °C. We, therefore, recommend analysts to be consistent in the LOI method used in relation to the ignition temperatures, exposure times, and the sample size and to include information on these three parameters when referring to the method.     

Loss on ignition: a qualitative or quantitative method for organic matter and carbonate mineral content in sediments?

Since the publication of the paper of , loss on ignition (LOI) has been widely used as a method to estimate the amount of organic matter and carbonate mineral content (and indirectly of organic and inorganic carbon) in sediments. The relationships between LOI at 550 °C (LOI₅₅₀) and organic carbon (OC) content and between LOI at 950 °C (LOI₉₅₀) and inorganic carbon (IC) content are currently accepted as a standard. However, the comparison of 150 analyses of samples of diverse lithologies, collected from a single core, reveals that these relationships are affected by sediment composition (presence of clays, salts, and the variable content of organic carbon). This results in an incremental error on the estimation of carbon content from LOI values that invalidates the use of LOI values as a quantitative method for estimating carbon content. Conversely, the general trends of LOI₅₅₀ and LOI₉₅₀ show a good correlation with carbon content (both organic and inorganic) allowing use of LOI as a qualitative test for carbon content. Similarly, in our case, LOI at 105 °C (LOI₁₀₅) is a good qualitative proxy for the trends in gypsum content.     

崇明东滩海三棱藨草生长期沉积物有机碳含量变化

The investigations on the organic carbon （OC） of core sediments were carried out in Chongming east tidal fiat （CM） during Scirpus mariqueter growing stage （from April to December 2004） in Yangtze Estuary. The Yangtze River annually transports a runoff discharge of 30,000 m^3/s, carrying about 480 million tons of sediments to the estuarine and coastal area, which formed a great OC pool. In the sampling spots, seven quadrats of 50 cm × 50 cm and five sediments cores of 20 cm deep （40 cm deep in December） were randomly established in order to collect vegetations and core sediments samples during the low tide each month except November. After pretreatment, the core sediments were sieved and their OC contents were measured according to the potassium dichromate method. The results show that the higher surface sediment OC content in summer comes from allochthonous terrigenous particle settlements on the Chongming east middle tidal fiat S. mariqueter zone. In autumn and winter, the decomposing of the defoliated S. mariqueter increases the surface sediments OC content. Settling velocity, sediment temperature and S. mariqueter growth are the main factors that can control the sediment carbon content. Summer is the “carbon losing” period of the tidal fiat sediments, while from September, it changes into the “carbon accumulating” period of sediment OC pool because of the decomposing of dead S. mariqueter community in the sediments. From this alternation of “carbon losing” period and “carbon accumulating” period, we conclude that carbon in the OC pool of the middle tidal fiat S. mariqueter zone sediments mainly comes from the atmospheric carbon rooted by S. mariqueter photosynthesis.     

Loss on ignition vs. thermogravimetric analysis: a comparative study to determine organic matter and carbonate content in sediments

Journal of Paleolimnology - Mass loss at specified temperatures has been used widely to determine amounts of organic matter and carbonate in sediment samples. The loss on ignition (LOI) method is...     

The variation of sediments organic carbon content in Chongming east tidal flat during Scirpus mariqueter growing stage

The investigations on the organic carbon (OC) of core sediments were carried out in Chongming east tidal flat (CM) during Scirpus mariqueter growing stage (from April to December 2004) in Yangtze Estuary. The Yangtze River annually transports a runoff discharge of 30,000 m3/s, carrying about 480 million tons of sediments to the estuarine and coastal area, which formed a great OC pool. In the sampling spots, seven quadrats of 50 cm × 50 cm and five sediments cores of 20 cm deep (40 cm deep in December) were randomly established in order to collect vegetations and core sediments samples during the low tide each month except November. After pretreatment, the core sediments were sieved and their OC contents were measured according to the potassium dichromate method. The results show that the higher surface sediment OC content in summer comes from allochthonous terrigenous particle settlements on the Chongming east middle tidal flat S. mariqueter zone. In autumn and winter, the decomposing of the defoliated S. mariqueter increases the surface sediments OC content. Settling velocity, sediment temperature and S. mariqueter growth are the main factors that can control the sediment carbon content. Summer is the "carbon losing" period of the tidal flat sediments, while from September, it changes into the "carbon accumulating" period of sediment OC pool because of the decomposing of dead S. mariqueter community in the sediments. From this alternation of "carbon losing" period and "carbon accumulating" period, we conclude that carbon in the OC pool of the middle tidal flat S. mariqueter zone sediments mainly comes from the atmospheric carbon rooted by S. mariqueter photosynthesis.     

Estimation of grain size variability with micro X-ray fluorescence in laminated lacustrine sediments,Cape Bounty,Canadian High Arctic

Finely laminated sediment cores from two Arctic lakes were investigated using the Itrax™ Core Scanner that provides micro X-ray fluorescence (μ-XRF) measurements with a spatial resolution of 100 μm. We compared these chemical measurements with standard geochemical methods using, at the macroscopic scale, inductively coupled plasma–atomic emission spectrometry (ICP-AES) and, at the microscopic scale, energy dispersive spectroscopy (EDS). We also investigated the relationship between the chemical profiles and the grain size of sediments at macro-scale using laser particle-size analysis, and at microscopic scale, using thin section image analysis techniques. Results show a link between grain size and the relative abundance of several elements. Silicon and zirconium are associated with very coarse silt and sand deposits, K and Fe with clay-rich layers, and Ti with silty facies. Four sedimentary facies are characterised based on sedimentary structure and texture, and interpreted in terms of known seasonal hydroclimatic processes. We show that is possible to identify these sedimentary facies using μ-XRF element abundance or ratio variations. The K/Ti ratio is the best marker of the upper varve boundary, and it might be used for varve identification and counting of Cape Bounty sediments in future. More generally, this study demonstrates new applications for paleohydrological reconstructions from laminated sediments.     

Estimation of soil organic carbon reservoir in China

The paper respectively adopted physio-chemical properties of every soil stratum from 2473 soil profiles of the second national soil survey. The corresponding carbon content of soils is estimated by utilizing conversion coefficient 0.58. In the second soil survey, the total amount of soil organic carbon is about 924.18×108t and carbon density is about 10.53 kgC/m2 in China according to the area of 877.63×106 hm2 surveyed throughout the country. The spatial distribution characteristics of soil organic carbon in China is that the carbon storage increases when latitude increases in eastern China and the carbon storage decreases when longitude reduces in northern China. A transitional zone with great variation in carbon storage exists. Moreover, there is an increasing tendency of carbon density with decrease of latitude in western China. Soil circle is of great significance to global change, but with substantial difference in soil spatial distribution throughout the country. Because the structure of soil is inhomogeneous, it could bring some mistakes in estimating soil carbon reservoirs. It is necessary to farther resolve soil respiration and organic matter conversion and other questions by developing uniform and normal methods of measurement and sampling.     

Estimation of soil organic carbon reservoir in China

1 IntroductionResearch on global change has aroused many scientists' attention to the balance, storage and spatial distribution of carbon in the terrestrial ecosystem. The carbon stored in soil is 2.5-3 times as much as that stored in plants[1,2], so the distribution and conversion of carbon in humus has become one of the global research foci on organic carbon at present[3]. Organic carbon and nitrogen contents in soils are not only important components of soils but also the most important eco…     

A first estimate of organic carbon storage in Holocene lake sediments in Alberta, Canada

This paper reports a first estimate of the Holocene lake sediment carbon pool in Alberta, Canada. The organic matter content of lake sediment does not appear to depend strongly on lake size or other limnological parameters, allowing a simple first estimate in which we assume all Alberta lake sediment to have the same organic matter content. Alberta lake sediments sequester about 15 g C m^-2 yr^-1, for a provincial total of 0.23 Tg C yr^-1, or 2.3 Pg C over the Holocene. Alberta lakes may represent as much as 1/1700 of total global, annual permanent carbon sequestration.     

全球主要河流流域碳酸盐岩风化碳汇评估

碳酸盐岩风化吸收的大气CO₂主要以HCO₃ ^-形式连续地经由河流从大陆输送到海洋,成为陆地生态系统的重要碳汇。目前主要河流流域的碳酸盐岩风化碳汇估算存在不确定性,分布格局尚不清晰。基于GEMS-GLORI全球河流数据库提供的全球10万km ²以上主要河流流域多年平均监测数据,利用水化学径流法估算出全球主要河流流域碳酸盐岩对CO₂的吸收速率为0.43±0.15 Pg CO₂ yr ^-1,平均CO₂吸收通量为7.93±2.8 t km ^-2 yr ^-1。CO₂吸收通量在不同气候带下差异显著,热带和暖温带CO₂年吸收速率占全球主要河流流域年吸收速率的62.95%。冷温带CO₂年吸收速率占全球主要河流流域的33.05%,仅次于热带地区。本文划分出全球CO₂吸收通量的9个关键带,关键带的交汇处CO₂吸收通量较高。喀斯特出露流域碳酸盐岩对CO₂吸收通量的均值为8.50 t km ^-2 yr ^-1,约为非喀斯特流域的3倍。全球喀斯特出露流域碳酸盐岩风化碳汇在全球碳循环、水循环及碳收支平衡估算研究方面占据重要地位。     

青海省土壤有机碳估算及其不确定性分析

土壤有机碳对区域碳平衡起着关键性的作用,量化其空间格局及动态变化是准确评估生态系统碳汇潜力的基础。然而,不同土壤有机碳估算方法和不同样本得出的结果存在非常大的差异和不确定性,尤其是地形复杂、对气候变化敏感的青藏高原地区。为定量评估不同方法估算的土壤有机碳密度空间分布格局在青藏高原地区的差异,论文以青海省为研究区,收集整理了青海省806个土壤有机碳密度采样点数据,基于气候、植被、地形和土壤等多种解释变量,采用逐步回归、反距离权重插值、普通克里格插值和随机森林模型4种不同的方法,对青海省表层(0～30 cm)土壤有机碳密度空间分布及其影响因素进行了探究。结果表明,归一化植被指数、光合有效辐射、总氮、年均温、海拔、年降水量和净初级生产力是土壤有机碳密度估算的重要变量;尽管4种方法所估算的青海省土壤有机碳密度的均值较为接近,处于5.14～5.62 kg C·m^-2之间,但其变化范围存在较大差异,分别为0.17～23.25、0.34～46.61、0.56～35.08和0.62～24.85 kg C·m^-2;4种方法模拟结果的均方根误差分别为3.93、3...     

Dissolved and total organic and inorganic carbon in some British rivers

Rivers transport both organic and inorganic carbon from their sources to the sea. Results of ~800 organic and inorganic analyses from various British rivers of contrasting size and land use are presented here: (1) the headwater River Tern, a rural river of 852 km² catchment; (2) the Ouseburn, a small urban 55 km² catchment; (3) the River Tyne, a larger river system of ~3000 km² catchment; (4) a spatial survey from 205 sample sites on ~60 rivers from SW England. We found that, with the exception of peat-rich headwaters, DIC concentration is always greater than DOC. DIC is primarily in the form HCO₃ ⁻ , with DIC concentrations highest in highly urbanised catchments, typically greater than those observed in catchments with carbonate bedrock, demonstrating a significant and previously unrecognised anthropogenic inorganic carbon input to urban rivers.     

荒漠草原碳酸盐岩土壤有机碳向无机碳酸盐的转移

通过在内蒙古中西部四子王旗荒漠草原土壤剖面采集土样,拟分析测定土壤有机碳(SOC)含量、土壤无机碳酸盐(SIC)含量和SIC的δ13C值,探讨SOC向SIC的迁移转化过程及其转移量。结果表明:随深度增加,SOC含量逐渐降低而SIC含量依次增大,SOC与SIC含量具有明显的负相关关系。随土层加深,SIC的δ13C值降低,在30 cm深度时相对最低为-8.6‰,而后增大,在深度为60 cm时其值为-5.8‰。说明通过"SOC—CO2—SIC"的微碳循环系统SOC向SIC发生碳的转移。应用碳稳定同位素技术和模型结合SIC的δ13C值对该研究区SIC进行区分,发现30~50 cm土层次生碳酸盐(PC)所占比例为58.5%,50~60 cm土层为44.2%。应用δ13C值对该地区SOC向SIC的转化碳量进行估算,该地区30~60 cm土层每千克土壤中大约固定了SOC分解转化的4.97~5.9 g CO2。     

Determination of carbon, carbonate, nitrogen, and phosphorus in freshwater sediments by near-infrared reflectance spectroscopy: Rapid analysis and a check on conventional analytical methods

Sediments are typically analyzed for C, N, and P for characterization, sediment quality assessment, and in nutrient and contaminant studies. Cost and time required for analysis of these constituents by conventional chemical techniques can be limiting factors in these studies. Determination of these constituents by near-infrared reflectance spectroscopy (NIRS) may be a rapid, cost-effective method provided the technology can be applied generally across aquatic ecosystems. In this study, we explored the feasibility of using NIRS to predict total C, CO₃ ^–2 organic C, N, and P in deep-water sediment cores from four Canadian lakes varying over 19 degrees of latitude. Concentration ranges of constituents in the samples (dry weight basis) were total C, 12-55; CO₃ ^–2, 6-26; organic C, 7-31; N, 0.6-3.1; and P, 0.22-2.1 mg g^–1. Coefficients of determination, r2, between results from conventional chemical analysis and NIR-predicted concentrations, based on calibrations across all the four lakes, were 0.97-0.99 for total C, organic C, and N. Prediction for CO₃ ^–2 was good for the hard water lake from a calibration across all four lakes, but this constituent in the three soft water lakes was better predicted by a calibration across the soft water lakes. The NIR calibration for P fell below acceptable levels for the technique, but proved useful in the identification of outliers from the chemical method that were later removed with the re-analysis of several samples. This study demonstrated that NIRS is useful for rapid, simultaneous, cost-effective analysis of total C, CO₃ ^–2, organic C, N, and P in dried sediments from lakes at widely varying latitudes. Also, this study showed that NIRS is an independent analytical tool useful for the identification of outliers that may be due to error during the analysis or to distinctive composition of the samples.     

Total N, total P and organic matters content in floodplain soils of Xianghai Nature Reserve

Soil sediment samples of 10 layers with a spacing of 10 cm each were collected in different floodplain zones adjacent to Huolin River in the Xianghai Nature Reserve, and contents of total N, total P and organic matters were analyzed. The results showed that contents of total N, total P and organic matters were generally decreasing with the increase of distance from sample locations to the river channel, and contents of the three items were generally higher in the upper soil layer than that in the lower soil layer. The content variations displayed how flooding functions influenced nutrient matter content variations in floodplain soils since the flood inundation frequencies of the sample locations varied. The correlation analysis displayed that there were remarkable relativities between total N, total P and organic matters within definite spatial distance from the Huolin River channel.