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1.
渤海东海海洋沉积物中碳氮稳定同位素标准物质研制 总被引：2，自引：2，他引：0
海洋沉积物中碳氮稳定同位素因其能够确定有机质的来源,有助于了解碳循环、气候变化、有机质迁移转化而备受关注,但其分析测试过程中尚缺乏海洋沉积物碳氮稳定同位素标准物质进行质量监控。本文依据ISO导则35和国家《一级标准物质技术规范》(JJG1006—1994),研制了三个海洋沉积物碳氮稳定同位素标准物质(MSCNI-1、MSCNI-2和MSCNI-3),候选物样品分别采自我国渤海锦州湾湿地、东海闽浙近岸和东海冲绳海槽,定值组分为总碳氮同位素(δ~(13)C-TC、δ~(15)N-TN)和有机碳氮同位素(δ~(13)C-C~(org)、δ~(15)N-N~(org)),定值方法采用元素分析-同位素比值质谱法(EA-IRMS)多家实验室协同定值。经检验,三个标准物质候选物均匀性良好,一年内定值组分均无显著变化,具有良好的稳定性;δ~(13)C和δ~(15)N的标准不确定度分别小于0.15%和0.24%,标准值和标准不确定度合理。该套标准物质是我国以海底沉积物为介质的基体型碳氮稳定同位素标准物质,定值方法准确可靠,可供海洋、地质及环境等相关领域实验室用于仪器校准、方法评价和质量监控等。 相似文献
2.
《矿物岩石地球化学通报》2017,(1)
为研究喀斯特地区土壤有机质的来源与演化,对贵州喀斯特地区黄壤剖面中黄土的有机质开展了碳同位素研究。结果表明,随着剖面深度加深,黄壤有机质及其中胡敏酸的δ~(13)C值趋于偏正,且有机质全样的δ~(13)C值高于胡敏酸。另外,胡敏酸超滤组分的δ~(13)C值随着分子量的减少而增大,说明分子量较低的胡敏酸中可能含更多富集~(13)C的组分,而分子量较大的胡敏酸中可能含更多贫~(13)C的组分。黄壤有机质的δ~(13)C值组成差异,反映了黄壤剖面有机质及胡敏酸形成过程中有碳同位素的分馏。 相似文献
3.
海洋沉积物中有机碳、氮稳定同位素(δ~(13)C、δ~(15)N)作为一种有效指标,可对不同地质时期空气、温度、降水等参数的变化进行标记。元素分析-同位素比值质谱法是一种测量海洋沉积物有机碳、氮稳定同位素组成的合理、有效的方法。目前我国有诸多实验室使用元素分析仪(EA)与稳定同位素比值质谱仪(IRMS)联用的方法对沉积物中的有机碳、氮稳定同位素进行测试。各实验室之间测试技术及数据稳定性缺少比对依据,测试结果缺乏有效的溯源,使用过程中缺乏规范和统一。本文选取了我国2018年研制的三个国家一级海洋沉积物碳氮稳定同位素标准物质(GBW04701、GBW04702、GBW04703)及两个国际标准物质(EMA-B2152、EMA-B2151),在我国十家实验室对EA-IRMS在线技术测试方法进行实验室间的测量比对实验,以验证方法的稳定性、精密度和准确度。测试结果表明:各家协作实验室的数据准确、稳定,方法的重复性和再现性良好,测得的δ~(13)C和δ~(15)N精密度分别好于0.10‰、0.14‰。通过比对研究,同时证明了EA-IRMS在线技术适用于海洋沉积物中的有机碳、氮稳定同位素的测定,初步建立了一套适合海洋沉积物样品分析的方法。 相似文献
4.
碳氮稳定同位素指示苔藓生境特征以及树冠对大气氮沉降的吸收 总被引：2，自引：0，他引：2
对贵阳地区一生境内不同生长条件(石生苔藓、无树冠、不同树冠类型以及同种树冠不同树冠厚度)下的细叶小羽藓(Haplocladium microphyllum(Hedw.)Broth)碳氮同位素进行了研究。不同生境的苔藓δ13C和δ15N值具有相似的变化趋势和明显的相关关系。石生苔藓δ13C和δ15N值比土生苔藓偏高指示了其相对干燥和受到干沉降控制的生境;树冠下方光照条件差、湿度高、缺少干沉降氮的输入是苔藓δ13C和δ15N值偏低的主要原因;而树冠类型、叶片形态、叶面性质造成树冠对大气沉降氮吸收能力的不同是三种树冠下方苔藓氮同位素组成差异的潜在因素。此外,同一树冠(桂花树Osmanthus fragrans Lour.)下方苔藓的氮含量和碳氮同位素平均组成与树冠厚度呈线性关系,尤其是δ15N的响应很好地反映了吸收过程中树冠厚度对大气沉降氮源同位素组成的控制作用。结果表明,苔藓δ13C值能很好地指示苔藓的生境差异和生理响应(如光合作用能力和氮需求等);而δ15N值在示踪氮源和反映不同树冠吸收过程的同位素分馏效应方面更具有优势,二者的相关关系是环境因素相互作用的重要线索。此外,细叶小羽藓Haplocladium microphyllum(Hedw.)Broth具有高效利用大气沉降氮和分布广泛等特点,可进一步应用于该地区大气氮沉降的指示或监测研究。 相似文献
5.
实验室和研究人员所使用的碳、氮同位素标准物质一般由国际原子能机构(IAEA)获得,然而近年来,随着碳氮同位素在实验室质量监控、方法评价、仪器校准等方面的广泛应用,市场需求量不断增加, IAEA研制的碳、氮同位素标准物质的种类与数量逐渐不能满足科学研究快速发展的需求。我国急需研制适应当今分析技术水平的有机质碳氮同位素国家标准物质用以进行质量监控、方法评价、仪器校准。为保证量值传递精度,本文研制了4个有机化学物质的碳氮稳定同位素标准物质,其中3个为尿素样品,1个为L-谷氨酸。经检验4种标准物质的均匀性通过F值检验,标准物质的δ~(13)C和δ~(15)N值经过一年的稳定性检验,特征量值变化在测量方法允许的不确定度范围内,由此判定δ~(13)C和δ~(15)N值稳定性良好。由包括研制单位实验室在内的12家实验室协同定值,采用高温燃烧-气体同位素质谱法测定了δ~(13)C和δ~(15)N值,系列标准物质δ~(13)C和δ~(15)N认定值区间呈梯度分布,δ~(13)C值为-40‰～0‰,δ~(15)N值为-10‰～30‰,涵盖了我国天然样品中有机质碳氮稳定同位素组成范围;研制的系列标准物质δ~(13)C的定值扩展不确定度不大于0.08‰,δ~(15)N的定值扩展不确定度不大于0.09‰,定值水平与国际标准物质相当。该系列标准物质已被国家质检总局批准为国家一级标准物质,批准号为GBW04494～GBW04497。可被用于地质、生态、环境等多种样品δ~(13)C和δ~(15)N比值测定时的分析监控、仪器校准、方法评价、质量保证和质量监控。 相似文献
6.
土壤有机质的碳同位素信息反映了上部的植被和气候状况，但植物体在被微生物分解、利用、转变为土壤有机质的过程中会产生碳同位素的分馏。本研究探了高山草甸和典型草原两种不同气候、生态环境条件下，植物转变为土壤有机质过程中的碳同位素组成变化。结果显示：在太白山高海拔地区的4个采样点，表土的δ13Corg值均随深度的增加而逐渐偏正，到距离地表10-15cm左右时，土壤的δ13Corg值基本稳定。经过长期分解稳定以后的土壤有机质的δ13C值要比其源植被约偏正1.65‰-2.27‰左右，平均约偏正1.9‰左右。在内蒙草原样地的4个采样点，亦表现出与太白山相似的变化：土壤样品的δ13Corg值从地表开始，随着深度的增加而逐渐偏正，到约距离地表10cm左右深度后，δ13Corg值逐渐达到稳定，在距地表10-16cm间基本稳定不变。在该深度土壤的δ13Corg值比它上面生长的植物的δ13C值要分别偏正1.3‰、1.4‰、1.4‰、1.2‰，4块样地平均偏正约1.3‰左右。本研究表明，在运用土壤有机碳同位素反淀古植被和古气候变化时，应考虑到不同气候、生态环境中植物转化为有机质过程中的碳同位素分馏影响。 相似文献
7.
沉积岩总有机质碳同位素分析的前处理影响 总被引：1，自引：0，他引：1
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。 相似文献
8.
氧化条件对样品有机碳同位素测定的影响因素讨论 总被引：1，自引：2，他引：1
有机碳同位素在全球变化、古气候和古环境恢复研究中的应用日益广泛和深人。有机碳同位素分析的基本原理是在高温下过量的氧气中将样品有机物氧化为CO2，通过分离纯化得到纯净的CO2气体送人质谱测定其护δ13C值。
在已发表文章中，对于有机碳同位素的研究，人们所采用的氧化温度和氧化时间都有很大差异，但很少系统地研究有机碳同位素分析氧化条件对样品有机碳同位素测定结果的影响。为了解不同的氧化条件是否会造成样品的有机碳同位素分馏，以及不同氧化条件对样品有机碳同位素测定结果的影响程度，笔者采用封管法，选取了不同类型的样品（有机碳标准、植物、表土、黄土以及红粘土等），采用不同的氧化温度：500℃,550℃,650℃,750℃,850℃,900℃以及950℃等，恒温2.5 h,然后炉冷至室温。
实验结果表明：氧化温度为850℃，恒温时间为2.5 h，对于有机碳标准、植物、表土和较年轻的黄土样品，足以确保样品有机质氧化充分，δ13C值达到稳定，不会产生同位素分馏。
但对于深层黄土和红粘土样品，氧化温度为850℃，恒温时间为2.5 h，其δ13C值不能达到一个稳定值，仍有偏正趋势。这可能是由于深层样品成岩化作用强，样品中含有一些含碳的矿物包裹体，随温度上升到一定程度，才逐渐分解，释放出气体。对于深层黄土和红粘土样品，采用850℃甚至更高的氧化温度其δ13C值仍未达到稳定，合适的氧化温度需进一步的研究来确定。 相似文献
9.
对南羌塘侏罗系布曲组和夏里组烃源岩氯仿沥青"A"组分碳同位素分析表明,碳同位素主要受有机母质及沉积环境影响,夏里组烃源岩氯仿沥青"A"组分的碳同位素较重,而布曲组烃源岩氯仿沥青"A"中族组分的碳同位素组成相对较轻。并且它们普遍存在碳同位素逆转现象,夏里组烃源岩氯仿沥青"A"组分的碳同位素逆转表现为:δ13C饱和烃δ13C非烃δ13C芳烃δ13C沥青质,主要受有机质母源控制;布曲组烃源岩氯仿沥青"A"组分的碳同位素逆转表现为:δ13C非烃δ13C沥青质δ13C饱和烃δ13C芳烃,主要与生物降解作用有关。 相似文献
10.
利用多环芳烃标准样品连续和穿插进样相结合的方式,检验了气相色谱-燃烧-同位素比质谱仪(GC-C-IRMS)测定多环芳烃单体碳同位素比值(δ13C)的稳定性和准确性,观察了测定过程中色谱柱的分离效果。结果表明,出峰面积和分离程度是影响化合物δ13C平行性的主要原因。通过多次实验,分析了样品前处理过程中多环芳烃各个化合物稳定碳同位素的分馏情况,包括凝胶渗透色谱(GPC)和硅胶柱等净化过程,以及旋转蒸发和氮气吹扫等浓缩过程。实验表明,各前处理过程中样品内多环芳烃的稳定碳同位素分馏均不明显,其中硅胶柱净化过程相比GPC过程对样品中多环芳烃的δ13C影响较大,但总体上仍未超过未处理标样δ13C值的2倍标准偏差范围。旋转蒸发和氮吹过程对样品中多环芳烃的δ13C影响程度相当,都位于未处理标样δ13C值1倍标准偏差以内的水平。 相似文献
11.
末次冰期以来南海北部下陆坡区沉积有机质地球化学特征及其意义 总被引：1，自引：0，他引：1
选取南海北部下陆坡-深海平原过渡带典型沉积柱状样,通过对其沉积有机质的整体有机地球化学特征进行表征,探讨了南海下陆坡-深海平原区沉积有机质在冰期/间冰期旋回中的赋存状态、来源变化以及与古气候环境之间的相应关系。结果表明,总有机碳（TOC）、总氮（TN）和有机质稳定碳同位素（δ13Corg）与冰期/间冰期旋回有明显的对应关系,冰期时对应高值,间冰期时对应低值;而有机质稳定氮同位素（δ15N）表现为全新世时其值偏低,末次冰消期其值偏高,与气候旋回没有相关性; C/N值和δ13Corg值都表明南海北部下陆坡沉积有机质来源是陆相和海相的混源,且在末次冰期/间冰期尺度上主要以海相来源为主。 相似文献
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Sylvain Huon Francis E. GroussetDidier Burdloff Gérard BardouxAndré Mariotti 《Geochimica et cosmochimica acta》2002,66(2):223-239
Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ13C, δ15N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ13C = −22.8 ± 1.0‰; δ15N = 5.5 ± 0.6‰). δ13C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ15N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL1, HL2, HL4, and HL5), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ13C (down to −28‰) and δ15N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL1, HL2, and with lesser extent for HL4. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL5, only the δ13C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL5 to HL1 (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ13C, increasing OC/TN and decreasing δ15N values. 相似文献
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《Gondwana Research》2014,25(3):1057-1069
The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ15NTN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ15NTN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ15N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the 15N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ13Ccarb and δ15NTN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO2 with recycled organic nitrogen. After the Shuram event, the δ15N value continued to decrease despite that δ13Ccarb rose back to + 4‰. The continued δ15N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ13Ccarb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ13Ccarb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions. 相似文献
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北京十三陵和天津蓟县两剖面中距今十四亿年海相碳酸盐岩的碳同位素表明,十三陵—蓟县地区当时具有较低的δ13C 值(共分析了152个样品),平均占δ13C=-0.7‰(PDB)。这种较低的δ13C 值很可能具有全球性。原始的海相碳酸盐岩较低的碳同位素组或反映较低的有机碳埋藏速率。有机碳的埋藏速率与当时全球生物量的大小有着密切的关系。磷酸盐岩较低的δ13C 值进一步反映当时较小的全球生物量的存在。每年8.11×108吨有机碳推测是距今十四亿年全球生物量的最小值。 相似文献
17.
Separation of total nitrogen from sediments into organic and inorganic forms for isotopic analysis 总被引：3，自引：0，他引：3
Nitrogen isotopic (δ15N) analysis is widely applied in palaeoceanography, palaeolimnology and soil science. Most measurements are performed on untreated bulk samples containing both organic and inorganic nitrogen (ON and IN), which could sometimes confound isotopic signals. Here we propose a sample pretreatment method to physically and quantitatively separate the total nitrogen into ON and IN for subsequent concentration and isotopic measurements. In the method, the sediment is first demineralized with HCl and HCl-HF, adsorbed and bound IN being liberated into the acid solutions during the demineralization. Then, organic matter (OM) dissolved in the acid solutions is recovered by a sorbent of styrene divinyl benzene polymer (Bond Elut PPL, Varian) and is then combined with the acid-resistant OM to obtain the total OM. Finally, IN in the acid solutions passing through the PPL sorbent is recovered by way of steam distillation. Total nitrogen recovery with the method is 92.4% and isotopic mass balance calculations show that the δ15N value of total nitrogen can be quantitatively partitioned into the organic and inorganic forms. The δ13C values of the separated OM show a small positive excursion of 0.2‰ relative to those of bulk OM, ruling out significant loss of ON during the pretreatment. By comparison, the KOBr method, widely used to remove ON from bulk samples for isotope measurements, gives lower IN concentration and higher δ15NIN values, attributed to the partial loss of IN and escape of some oxidation-resistant ON. 相似文献
18.
Moritz F Lehmann Stefano M BernasconiAlberto Barbieri Judith A McKenzie 《Geochimica et cosmochimica acta》2002,66(20):3573-3584
The carbon and nitrogen isotope composition of organic matter has been widely used to trace biogeochemical processes in marine and lacustrine environments. In order to reconstruct past environmental changes from sedimentary organic matter, it is crucial to consider potential alteration of the primary isotopic signal by bacterial degradation in the water column and during early diagenesis in the sediments.In a series of oxic and anoxic incubation experiments, we examined the fate of organic matter and the alteration of its carbon and nitrogen isotopic composition during microbial degradation. The decomposition rates determined with a double-exponential decay model show that the more reactive fraction of organic matter degrades at similar rates under oxic and anoxic conditions. However, under oxic conditions the proportion of organic matter resistent to degradation is much lower than under anoxic conditions. Within three months of incubation the δ13C of bulk organic matter decreased by 1.6‰ with respect to the initial value. The depletion can be attributed to the selective preservation of 13C-depleted organic compounds. During anoxic decay, the δ15N values continuously decreased to about 3‰ below the initial value. The decrease probably results from bacterial growth adding 15N-depleted biomass to the residual material. In the oxic experiment, δ15N values increased by more then 3‰ before decreasing to a value indistinguishable from the initial isotopic composition. The dissimilarity between oxic and anoxic conditions may be attributed to differences in the type, timing and degree of microbial activity and preferential degradation. In agreement with the anoxic incubation experiments, sediments from eutrophic Lake Lugano are, on average, depleted in 13C (−1.5‰) and 15N (−1.2‰) with respect to sinking particulate organic matter collected during a long-term sediment trap study. 相似文献
19.
Stable nitrogen isotope analysis is a fundamental tool in assessing dietary preferences and trophic positions within contemporary and ancient ecosystems. In order to assess more fully the dietary contributions to human tissue isotope values, a greater understanding of the complex biochemical and physiological factors which underpin bulk collagen δ15N values is necessary. Determinations of δ15N values of the individual amino acids which constitute bone collagen are necessary to unravel these relationships, since different amino acids display different δ15N values according to their biosynthetic origins. A range of collagen isolates from archaeological faunal and human bone (n = 12 and 11, respectively), representing a spectrum of terrestrial and marine protein origins and diets, were selected from coastal and near-coastal sites at the south-western tip of Africa. The collagens were hydrolysed and δ15N values of their constituent amino acids determined as N-acetylmethyl esters (NACME) via gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). The analytical approach employed accounts for 56% of bone collagen nitrogen. Reconstruction of bulk bone collagen δ15N values reveals a 2‰ offset from bulk collagen δ15N values which is attributable to the δ15N value of the amino acids which cannot currently be determined by GC-C-IRMS, notably arginine which comprises 53% of the nitrogen unaccounted for (23% of the total nitrogen). The δ15N values of individual amino acids provide insights into both the contributions of various amino acids to the bulk δ15N value of collagen and the factors influencing trophic position and the nitrogen source at the base of the food web. The similarity in the δ15N values of alanine, glutamate, proline and hydroxyproline reflects the common origin of their amino groups from glutamate. The depletion in the δ15N value of threonine with increasing trophic level indicates a fundamental difference between the biosynthetic pathway of threonine and the other amino acids. The δ15N value of phenylalanine does not change significantly with trophic level, reflecting its conservative nature as an essential amino acid, and thus represents the isotopic composition of the nitrogen at the base of the food web. Δ15NGlu-Phe values in particular are shown to reflect trophic level nitrogen sources within a food web. In relation to the reconstruction of ancient human diet the contribution of marine and terrestrial protein are strongly reflected in Δ15NGlu-Phe values. Differences in nitrogen metabolism are also shown to have an influence upon individual amino acid δ15N values with Δ15NGlu-Phe values emphasising differences between the different physiological adaptations. The latter is demonstrated in tortoises, which can excrete nitrogen in the form of uric acid and urea and display negative Δ15NGlu-Phe values whereas those for marine and terrestrial mammals are positive. The findings amplify the potential advantages of compound-specific nitrogen isotope analysis in the study of nitrogen flow within food webs and in the reconstruction of past human diets. 相似文献
20.
James W. Fourqurean Susie P. Escorcia William T. Anderson Joseph C. Zieman 《Estuaries and Coasts》2005,28(3):447-461
Elemental and isotopic composition of leaves of the seagrassThalassia testudinum was highly variable across the 10,000 km2 and 8 years of this study. The data reported herein expand the reported range in carbon:nitrogen (C:N) and carbon:phosphorus (C:P) ratios and δ13C and δ15N values reported for this species worldwide; 13.2–38.6 for C:N and 411–2,041 for C:P. The 981 determinations in this study generated a range of ?13.5‰ to ?5.2‰ for δ13C and ?4.3‰ to 9.4‰ for δ15N. The elemental and isotope ratios displayed marked seasonality, and the seasonal patterns could be described with a simple sine wave model. C:N, C:P, δ13C, and δ15N values all had maxima in the summer and minima in the winter. Spatial patterns in the summer maxima of these quantities suggest there are large differences in the relative availability of N and P across the study area and that there are differences in the processing and the isotopic composition of C and N. This work calls into question the interpretation of studies about nutrient cycling and food webs in estuaries based on few samples collected at one time, since we document natural variability greater than the signal often used to imply changes in the structure or function of ecosystems. The data and patterns presented in this paper make it clear that there is no threshold δ15N value for marine plants that can be used as an unambiguous indicator of human sewage pollution without a thorough understanding of local temporal and spatial variability. 相似文献