Extraction and identification of elemental carbon in sediment and its environmental and climatic implications

Elemental carbon was extracted from sediments by chemical oxidation and identified by Raman spectroscopy. The experimental results indicate that elemental carbon, defined by processing, is a continuum ranging from single crystal graphite to amorphous carbon. Chemical oxidation is a feasible method to extract elemental carbon from sediments, and when experimental condition and time are properly controlled, it can remove organic carbon without any loss of elemental carbon. However, due to the differences in experimental conditions and methods, different results have been obtained. Therefore, we believe that the determination of standard sample and its concentration as well as the unification of the experimental method are of great importance. Also, the unification and definition of all these carbon particulates can facilitate transect comparison and further research in related fields. In profile research, elemental carbon was extracted and determined by using the same method. The elemental carbon curve tends to change with other climatic proxies, indicating elemental carbon can provide another new proxy for climatic and environmental changes. Based on the analysis, we deduce that the elemental carbon record has different implications for climate and environmental changes on different time-scales. __________ Translated from Acta Sedimentologica Sinica, 2007, 25(5): 745–752 [译自: 沉积学报]     

石家庄地区地下水中溶解性有机碳同位素特征及其环境指示意义

溶解性有机碳(DOC)是地下水中微生物代谢活动的主要能量来源,δ13CDOC值是指示DOC来源及生物代谢活动的重要参数.通过对石家庄地区浅层地下水中DOC浓度及δ13CDOC特征进行分析,结合相应的水化学检测,探讨了δ13CDOC值对地下水环境演化的指示作用.结果表明:DOC浓度及其同位素特征均受到天然及人为两方面影响,表现出一定的空间特征.在垂向上,除石家庄西北部地区以外,研究区地下水中DOC浓度随地下水埋深的增大有降低趋势,δ13CDOC随地下水埋深的增大而增大;石家庄西北部地区具有一定特殊性,地下水埋深较浅,交替强烈,TOC含量较高,而DOC浓度较低,δ13CDOC值偏负.在水平方向上,滹沱河沿岸地区,沿地下水流向,DOC浓度逐渐降低,δ13CDOC值逐渐偏正.石家庄南部地区受污灌影响,DOC浓度较高,δ13CDOC值偏负.研究区地下水埋藏深度、补给条件、径流特征以及人为作用均对地下水中DOC浓度及其同位素特征产生显著影响.δ13CDOC值与SO42-、NO3-浓度的相关关系指示出研究区地下水中反硝化作用和硫酸盐还原作用的发生,从吴家营、宋营一带开始逐渐由硝酸盐还原环境向硫酸盐还原环境过渡;沿地下水流向,地下水环境还原程度增强.     

Precambrian sedimentary carbonates: carbon and oxygen isotope geochemistry and implications for the terrestrial oxygen budget

Carbon isotope values of 260 Precambrian limestones and dolomites (most of them being substantially unaltered) have yielded an overall mean of $\text{δ}{}^{13}\text{C}\text{= +0.4 ± 2.7‰}$ vs. PDB; the corresponding oxygen values average at $\text{δ}{}^{13}\text{O = +20.0 ± 4.2‰}$ vs. SMOW. Like the overall mean, the δ ¹³C values furnished by individual carbonate occurrences are, as a rule, fairly “modern” and almost constant as from the very beginning of the sedimentary record. A remarkable exception are the “heavy” dolomites of the Middle Precambrian Lomagundi Group, Rhodesia, with $\text{δ}{}^{13}\text{C}\text{= +9.4 ± 2.0‰}$ vs. PDB. As a result of our measurements, the sporadic occurrence in the geological past of anomalously heavy carbonates seems to be established.The approximate constancy around zero per mill of the δ ¹³C values of marine carbonates through geologic time would imply a corresponding constancy of the relative proportion of organic carbon in the total sedimentary carbon reservoir since about 3.3 · 10⁹ y ago (with C_org/C_total ? 0.2). Utilizing this ratio and current models for the accumulation of the sedimentary mass as a function of time, we get a reasonable approximation for the absolute quantity of organic carbon buried in sediments and, accordingly, of photosynthetic oxygen released. Within the constraints of our model (based on a terrestrial degassing constant λ = 1.16 · 10^?9 y^?1) close to 80% of the amount of oxygen contained in the present oxygen budget should have been released prior to 3 · 10⁹ y ago. Since geological evidence indicates an O₂-deficient environment during the Early and most parts of the Middle Precambrian, there is reason to believe that the distribution of this oxygen between the “bound” and the “molecular” reservoir was different from that of today (with effective O₂-consuming reactions bringing about an instantaneous transfer to the crust of any molecular oxygen released). Accordingly, the amount of C_org in the ancient sedimentary reservoir as derived from our isotope data is just a measure of the gross amount of photosynthetic oxygen produced, withholding any information as to how this oxygen was partitioned between the principal geochemical reservoirs. As a whole, the carbon isotope data accrued provide evidence of an extremely early origin of life on Earth since the impact of organic carbon on the geochemical carbon cycle can be traced back to almost 3.5 · 10⁹y.     

Evidence of climatic change from oxygen and carbon isotope variations in sediments of a small arctic lake,Canada

Radiocarbon dating of the organic-rich sediments of Lake Illisarvik in the outer Mackenzie Delta indicates that formation of the lake occurred approximately 9500yr BP, with maximum expansion around 6000 yr BP. Sedimentation rates have remained relatively constant at an average of 0.3mm/yr. ¹³C results on biogenic and inorganic carbonates and organics indicate a change from dominantly terrestrial organics (?27 to ?28%₀) to submerged aquatic vegetation or plankton (?18 to ?23%₀) upon formation of the lake (9500yr BP), and a dramatic return to dominantly terrestrial organics at 5800yr BP (δ¹³C = ?27 to ?30%₀). This latter shift is accompanied by a drastic reduction in the macroflora and fauna populations. ¹⁸O results suggest that a warmer climate than today existed prior to the shift at 5800yr BP.     

沁水煤层气田高阶煤解吸气碳同位素分馏特征及其意义

沁水盆地是我国煤层气勘探开发的重要有利区,沁水煤层气田位于盆地东南部。对采自沁水煤层气田两口井的煤开展了罐解吸实验。结果表明,该地区煤层气解吸速率很快,96 h后解吸气量都达到了总解吸气量的60%~85%,720 h后解吸过程基本结束;解吸气量大,平均在18 m3/t以上。煤层气解吸过程中甲烷发生碳同位素分馏,δ13C1值变化与解吸率呈良好的线性关系,参考这种正相关关系曲线,定期监视煤层气降压排采过程中甲烷δ13C1值的变化情况,可以大致推测出该地区煤层气解吸率,从而预测煤层气的采出程度。跟踪测试沁水煤层气田A1和A1-3井在试采过程的甲烷δ13C1变化情况,推测现在采出的煤层气可能主要是煤层裂隙中以游离形式存在的煤层气,表明该区煤层气稳产性较好,资源前景广阔。     

鄱阳湖沉积物近8ka来有机质碳同位素记录及其古气候变化特征

通过对鄱阳湖沉积物的高密度采样和有机质碳同位素分析,讨论了鄱阳湖近 8 ka来的古气候环境.鄱阳湖沉积物有机质δ 13C值为-22.42‰～-32.42‰,属 C3类植物来源.暖湿期δ 13C值相对偏负;冷(凉)干期δ 13C值相对偏正.这些记录表明,鄱阳湖近 8 ka来经历了 4次暖湿和 4次冷(凉)干的气候环境变化, 7 900～3 660 a B.P.、3 440～2 990 a B.P.、2 940～2 170 a B.P.、1 820～6 50 a B.P.属相对温暖湿润的气候环境;3 660～3 440 a B.P.、2 990～2 940 a B.P.、2 170～1 820 a B.P.、650～200 a B.P.为相对冷凉干旱的气候环境,自 200 a B.P.(1 750 A.D.)以来湖区气候开始转暖.暖湿期持续时间较长,冷(凉)干期持续时间较短,1 000 a B.C.左右为一次重要的气候变冷事件.我国全新世几个特征性气候在湖区均有不同的显示,并与孢粉、硅藻、历史记录所反映的古气候环境对应性较好,可以作为恢复古气候变化的灵敏指标.     

Field,petrophysical and carbon isotope studies on the Lapland Granulite Belt: implications for deep continental crust

The Palaeoproterozoic Lapland Granulite Belt is a seismically reflective and electrically conductive sequence of deep crustal (6–9 kbar) rocks in the northern Fennoscandian Shield. It is composed of garnet-sillimanite gneisses (khondalites) and pyroxene granulites (enderbites) which in certain thrust sheets form about 500 m thick interlayers. The structure was formed by the intrusion of intermediate to basic magmas into turbiditic sedimentary rocks under granulite facies metamorphism accompanied by shearing of the deep crust about 1.93–1.90 Gyr ago (Gal. Granulites were upthrust 1.90–1.87 Ga and the belt was divided by crustal scale duplexing into four structural units whose layered structure was preserved. The thrust structures are recognized by the repetition of lithological ensembles and by discordant structural patterns well distinguishable in airborne magnetic and electromagnetic data. Thrusting gave rise to clockwise pressure-temperature evolution of the belt. However, some basic rocks possibly record an isobaric cooling path. The low bulk resistivity of the belt (200–1000 Ωm) is caused by interconnected graphite and subordinate sulphides in shear zones. On the basis of carbon isotope ratios this graphite is derived mostly from sedimentary organic carbon. The seismic reflectivity of the belt may be caused by velocity and density differences between pyroxene granulites and khondalites, as well as by shear zones.     

A molecular and carbon isotope biogeochemical study of biomarkers and kerogen pyrolysates of the Kimmeridge Clay Facies: palaeoenvironmental implications

Structures and carbon isotopic compositions of biomarkers and kerogen pyrolysis products of a dolomite, a bituminous shale and an oil shale of the Kimmeridge Clay Formation (KCF) in Dorset were studied in order to gain insight into (i) the type and extent of water column anoxia and (ii) changes in the concentration and isotopic composition of dissolved inorganic carbon (DIC) in the palaeowater column. The samples studied fit into the curve of increasing δ¹³C of the kerogen (δ¹³C_TOC) with increasing TOC, reported by Huc et al. (1992). Their hypothesis, that the positive correlation between TOC and δ¹³C_TOC is the result of differing degrees of organic matter (OM) mineralisation in the water column, was tested by measuring the δ¹³C values of primary production markers. These δ¹³C values were found to differ on average by only 1‰ among the samples, implying that differences in the extent of OM mineralisation cannot fully account for the 3‰ difference in δ¹³C_TOC. The extractable OM in the oil shale differs from that in the other sediments due to both differences in maturity, and differences in the planktonic community. These differences, however, are not likely to have significantly influenced δ¹³C_TOC either. All three sediments contain abundant derivatives of isorenieratene, indicating that periodically euxinia was extending into the photic zone. The sediments are rich in organic sulfur, as revealed by the abundant sulfur compounds in the pyrolysates. The prominence of C₁-C₃ alkylated thiophenes over n-alkanes and n-alkenes is most pronounced in the pyrolysate of the sediment richest in TOC. This suggests that sulfurisation of OM may have played an important role in determining the TOC-δ¹³C_TOC relationship reported by Huc et al. (1992).     

四川盆地晚奥陶世有机碳、氮同位素异常及其古环境意义

晚奥陶世全球海洋环境曾发生重要的改变,特别是赫南特冰期的气候变冷,造成了古海洋沉积物中多项地球化学指标出现异常现象,全球多地区出露的赫南特阶均记录了冰期时出现的碳、氮同位素异常,但对其产生机制的认识存在争议。四川盆地东南缘三泉剖面和双河剖面的奥陶系五峰组、观音桥段以及志留系龙马溪组的有机碳同位素、总氮同位素等地球化学指标测试结果显示,三泉剖面和双河剖面的赫南特阶观音桥段泥灰岩有机碳同位素和总氮同位素均出现正偏偏移,并可与其他地区奥陶系剖面进行对比。其中,三泉剖面δ¹³Corg值分布范围为-31.9‰～-27.9‰,自五峰组顶部开始偏重,在观音桥段达到峰值-27.9‰,偏移幅度约2‰;双河剖面δ¹³Corg平均值为-30.1‰,观音桥段最大值为-29.1‰,向正偏移幅度约为1‰左右。这些变化特征揭示,晚奥陶世有机质的埋藏作用可能改变了海洋溶解无机碳库的碳同位素组成,并且引起赫南特冰期碳同位素异常。三泉剖面和双河剖面δ¹⁵N平均值分别为1.4‰和1.1‰,冰期观音桥段δ¹⁵N值正偏幅度在0.5‰～1‰之...     

A solution for the northern hemisphere climatic zonation during a glacial maximum

The same model previously used to deduce an acceptable first order picture of the present zonally averaged macroclimate is now solved for the climatic response to the “glacial” surface boundary conditions that prevailed at 18,000 BP in the northern hemisphere. The equilibrium solution obtained gives the distributions with latitude of the mean temperature, wind, humidity, precipitation, evaporation, heat balance, transient baroclinic eddy statistics (i.e., kinetic energy of the meridional wind and meridional flux of heat, momentum, and water vapor), and the energy integrals. In general terms, the solution shows the glacial atmosphere to be colder and drier than at present, with an intensified polar front, stronger mean zonal and poloidal winds, more intense transient baroclinic eddies (storms) transporting heat, momentum and water vapor poleward at higher rates, and reduced precipitation and evaporation. Also evident is an equatorward shift of the climatic zones (as delineated by the mean surface zonal winds, the poloidal motion, and the difference between mean evaporation and precipitation), particularly in higher latitudes. Other properties of the solution, such as the effect of zonal wind changes on the length of the day, are discussed.     

Oxygen,carbon and strontium isotope systematics in two profiles across the Glarus thrust: implications for fluid flow

. The Glarus thrust is a prominent tectonic feature in the eastern Helvetic Alps. It has been recognized as a potential major pathway for syntectonic crustal scale fluid flow. The oxygen, carbon and strontium isotope patterns obtained from two vertical profiles across the thrust indicate fundamentally different flow regimes in the southern section of the thrust, where the footwall is represented by Mesozoic limestones, and in the northern section, where the footwall is represented by Tertiary flysch. At the Grauberg locality in the south, the observed isotope patterns give evidence of a net mass transport component from the hanging wall Verrucano to the footwall limestone with a maximum time-integrated volumetric fluid flux of 6.1 m³/m² In the south, the hydration of the lowermost 10 to 20 m of the hanging wall Verrucano requires introduction of an aqueous fluid by subhorizontal flow along the thrust with a minimum time integrated flux of 240 m³/m². At the Lochseite locality in the north, the isotope patterns indicate a vertical mass transport component from the footwall flysch to the hanging wall Verrucano with a time-integrated fluid flux of 2.6 m³/m². In the north, the fluids were probably derived from compaction and dehydration of the footwall flysch during thrusting. The ascending fluids were ponded below the Verrucano and 'lubricated' the thrust. Short-term pressure drops associated with seismic motion along the thrust led to the precipitation of calcite in veins at the thrust surface contributing material to the Lochseiten calc-mylonite, a thin calc-mylonite layer at the thrust contact. Although cross thrust fluid flow may have been two to three orders of magnitude smaller than flow along the thrust, it had a major impact on the isotopic composition of the Lochseiten calc-mylonite. In particular, it buffered the oxygen isotope composition of the calc-mylonite towards the relatively ¹⁸O-depleted composition of the hanging wall Verrucano in the south and towards the relatively ¹⁸O-enriched compositions of the footwall flysch in the north. By this mechanism a regional south to north ¹⁸O-enrichment trend was simulated within the Lochseiten calc-mylonite.     

The deglaciation history of the Lake Superior region and its climatic implications

A zone of synchronous end moraines has been recognized in the Lake Superior region across northern Ontario and Michigan. The moraines were formed between 11,000 and 10,100 y.a. as cold climate resulted in successive halts in the general ice retreat. The cold climate is also indicated by the presence of tundra near Lake Superior until about 10,000 y.a. This episode is here referred to as the Algonquin Stadial. It was preceded and followed by rapid deglaciation. The Algonquin Stadial is comparable in age with the Younger Dryas Stadial of Europe, and indicates a reversal in the continuous trend toward a warmer climate during Late-Wisconsin (an) time. The apparent conflict between the present result (based on geologic evidence) and earlier pollen stratigraphical studies with no reversal is discussed.Glacial Lake Duluth formed in the western Lake Superior basin before 11,000 BP, followed by a series of Post-Duluth lakes between approximately 11,000 and over 10,100 BP. The Main Lake Algonquin stage in the Huron and Michigan basins terminated approximately 11,000 BP. The subsequent high-level post-Main Algonquin lakes, which were contemporaneous with the Post-Duluth lakes, existed in the southeastern Lake Superior basin. When the ice margin was along the north shore 9500 BP Lake Minong occupied the whole Lake Superior basin. By 9000 BP the ice had retreated north of Lake Superior-Hudson Bay divide.     

A Ce/Nd isotope study of crustal contamination processes affecting Palaeocene magmas in Skye,Northwest Scotland

Twelve¹³⁸Ce/¹³⁶Ce isotope determinations, 31 Nd isotope analyses, and 31 REE profiles are presented for Tertiary basic to intermediate igneous rocks from the Isle of Skye, NW Scotland. The aim of this work is to precisely identify the contamination mechanisms of basic magmas emplaced through old crust, and to test the effectiveness of Ce isotope analysis as a petrogenetic tool.Combined Ce/Nd isotope analysis enables the modelling of the light REE profiles of the mantle-derived precursors to contaminated lavas, using different crustal end-members, in order to compare these with the magmatic lineage of uncontaminated Skye lavas. The geochemical data support a contamination mechanism involving a granitic melt, produced either by large degree melting of Scourian granulitefacies acid sheets, or (possibly) by melting of intermediate gneiss out of isotopic equilibrium.Basaltic lavas showing strong isotopic contamination effects yield calculated degrees of crustal contamination by large degree granitic melts of ca. 8 or 9% based on Ce and Nd isotopic data respectively. However, for lavas with liquidus temperatures of over 1250° C, the temperature dependence of the degree of contamination is weak.The combination of this evidence with new and published Pb isotope data suggests that the bulk of crustal contamination of the Skye lavas occurred in sill complexes at distinct levels in the crust, rather than during the actual ascent of magma through the crust in dykes. It is suggested on the basis of published fluid dynamic and field evidence that the assimilation of large degree melts of acid gneiss by turbulently flowing magma is more likely than assimilation of small degree disequilibrium melts from more refractory intermediate gneisses.It is concluded that Ce isotope analysis is a viable and useful adjunct to Nd isotope data in petrogenetic studies of continental igneous rocks emplaced through old basement.     

A Lateglacial and Holocene organic carbon isotope record of lacustrine palaeoproductivity and climatic change derived from varved lake sediments of Lake Holzmaar,Germany

A composite varve-dated 11.4 m long sediment sequence from Lake Holzmaar, situated in the Eifel region of western Germany, was investigated for total organic matter content, total nitrogen content and stable organic carbon isotopes. Mean time resolution is 75 years for TN and 14 years for δ¹³C_org. On millennial time scales primary production of lacustrine algae strongly depends on the delivery of nutrients from the catchment. The respective carbon isotope record is characterized by marked variations of δ¹³C_org ranging from −36.0‰ to −27.0‰ and includes a number of pronounced shifts. Reactions of the lacustrine system and the catchment to changes of environmental parameters, e.g. runoff, solar radiation and temperature, induce changes of algal associations and of lacustrine primary production which are reflected in the sediments as carbon isotope variations. Clear evidence of ecosystem reorganizations is detected by the carbon isotope record around 14,200, 10,400, 9600, 5500, 2700, 1700 and 900 varve years BP. In particular, the Holocene events of 9600, around 5500 and 2700 are interpreted as the expression of massive changes of the climate system. The steady rise of δ¹³C_org values during the mid-Holocene is interpreted as a continuous climatic amelioration reaching an optimum around 6500 varve years BP. Rapid and large changes of δ¹³C_org values from 2700 varve years BP to the present indicate major disturbances in the catchment area. These are most probably related to deforestation or reforestation and runoff changes, presumably in conjunction with human impact. Carbon isotopes, thus, characterize the Holzmaar ecosystem in time revealing lacustrine palaeoproductivity as well as providing palaeoenvironmental and palaeoclimatic information.     

Variability of organic carbon isotope and C/N in the Hemudu Area,Hangzhou Bay and its environmental implications in the Holocene

With the purpose of tracing the variations of the organic matter sources of sediments, a sample column (25.96 m in size) from the Hemudu Area of Hangzhou Bay was put through AMS¹⁴C dating and biogeochemical analysis. TOC and TN presented similar variation trends, suggesting the same and stable sources of organic matter; the bad correlation between the grain size and TOC content indicated that the organic matter occurrence was neither controlled by the grain size nor the surface absorption of the fine particles, but it may has something to do with the complicated sedimentary hydrodynamic force, the input of organic matter and microbial action. Judging on the basis of C/N ratio and δ¹³C_TOC, the organic carbon in sediments was a mixture of terrigenous and marine organic carbon, testifying to the land-sea interaction characteristic of the study area. The indexes experienced abrupt changes at about 6.5 ka BP, when the lighter terrigenous organic carbon made an increased proportion to the heavier marine organic carbon. The phenomenon reflected the enclosure of the lagoon and the reduced exchange interactions with the seawater of open seas.     

37 ka以来日本海沉积物有机质碳和氮稳定同位素变化及其古海洋学意义

海洋沉积物有机质碳氮稳定同位素(δ¹³C、δ¹⁵N)广泛用于有机质来源示踪、古生产力和古海洋环境重建。日本海沉积物δ¹³C和δ¹⁵N值一个显著特征是在末次冰盛期(LGM)同步负偏,但是对这一现象产生的原因以及他们的演化过程的认识仍然存在明显不足。在本研究中,我们详细调查了37 ka以来日本海中部LV53-23-1岩心沉积物δ¹³C和δ¹⁵N演化历史。结果显示,沉积物δ¹³C和δ¹⁵N分别介于-26.3‰至-22.5‰和1.6‰至6.1‰,低值出现在LGM(26.5~17 ka)暗色层状泥发育时期,指示较强的陆源输入贡献。在Heinrich冰阶1时期(17~14.5 ka),δ¹³C和δ¹⁵N快速正偏,表明日本海海洋环境发生了明显的转换,对应于对马海峡淹没及对马暖流入侵。14.5 ka之后,沉积物δ¹⁵N值恢复到5‰,与开阔大洋海水硝酸盐的δ¹⁵N值近似。我们采用二端员混合模型粗略地估算了有机质来源的相对贡献。LGM时期陆源有机质贡献介于65%至80%,14.5 ka以后海源有机质贡献介于60%至80%。除了增加的陆源有机质贡献以外,LGM时期沉积物δ¹⁵N亏损还涉及如下过程:(1)较高的含Fe沙尘供给提高日本海表层海洋生物固氮效率;(2)缺氧环境盛行减弱成岩作用对沉积物δ¹⁵N影响。37 ka以来,日本海沉积物δ¹³C和δ¹⁵N变化与有机质来源、营养盐的供给、表层生产力和沉积物氧化还原条件相关,实际受海平面和全球气候制约。     

亚洲季风区降水中稳定同位素气候意义研究进展

文章回顾了过去30多年围绕亚洲季风区,特别是青藏高原降水与冰芯同位素现代过程研究,对季风区稳定同位素气候意义的认识过程。降水及不同介质氧稳定同位素研究从最早聚焦于降水同位素与当地气候因子之间的关系,即"温度效应"与"降水量效应",发展到大尺度大气环流过程对降水同位素时空变化的影响,进而否定了局地气候因子的控制作用。近些年重要的研究进展之一是明确了与赤道海洋温度变化相关的ENSO对整个亚洲季风区同位素年际年代际波动的影响过程与机制,发现了大尺度大气环流在不同时间尺度稳定同位素记录中的显著信号。这些认识对于亚洲季风区冰芯、石笋、树轮同位素气候意义的解释都具有重要意义。但在不同时间尺度上,影响降水同位素的主导控制因素不同,导致对于解释长时间尺度同位素记录仍存在挑战,有待于从机制和结合同位素分馏的大气环流模型模拟研究中取得新的突破。     

Spatial and temporal stability of the climatic signal in northern Fennoscandian pine tree-ring width and maximum density

The spatial and temporal stability of the climatic signal in pine tree - ring width and maximum density is examined using data from four sites in northern Sweden and Finland. Moving-window multiple linear regression, using monthly and daily climate data, indicates that ring widths at all sites have been strongly controlled by July temperatures throughout the past century. The relationship between maximum density and temperature is stronger but much less stable across both space and time. Shifts in the hottest part of the summer do not explain large shifts in the period most strongly influencing density. It is concluded that palaeoclimate reconstructions based on northern Fennoscandian pine tree - ring width chronologies should be restricted to the temperature of midsummer (July), whereas maximum density should be used to reconstruct the temperature of a longer growth season (June to August). They thus provide different and compl e mentary palaeoclimate signals. At all four sites, the correlation between maximum density and June to August mean temperature is lowest in the latter half of the 20th century, but split sample tests with strong verification statistics (RE and CE) show that this represents a quantitative change in the strength of the correlation with climate, rather than a qualitative change in the nature of that relationship, and thus does not invalidate climate reconstructions.