Major Element Data (1966–1978) for The Six "Nimroc" Reference Samples

The results are given for all the determinations made by the co-operating laboratories of major elements in the six NIMROC rock samples (granite, syenite, lujavrite, norite, pyroxenite and dunite) prepared by the National Institute for Metallurgy in 1966. Relevant statistical data are given for the sets of results for each major constituent, and recommended values for all constituents except Al₂0₃, Na₂0, K₂0and CO₂ in dunite, Fe₂O₃, MgO and CO₂ in the granite, Fe₂₃ and CO₂ in the norite and CO₂ in the pyroxenite.
This report and that on the trace and minor elements issued in 1978 complete the revision of the recommended values. It is suggested that analysts should concentrate rather on those constituents for which the results have shown such a wide scatter that they can be of no usc for reference purposes, than on those for which the ualues are fairly well established.     

青藏高原东部长江流域盆地地表化学剥蚀通量剥蚀速率大气CO2净消耗率研究

2000-2002年期间,笔者对青藏高原东部长江流域溶质载荷分别进行了取样分析并对流域盆地化学剥蚀通量、剥蚀速率和大气CO2净消耗率进行了计算。结果表明,流域盆地化学剥蚀速率以河源区楚玛尔河最高为2.34×10^6mol/a/km^2,沱沱河最低为1.40×10^6mol/a/km^2,四大支流雅砻江为1.69×10^6mol/a/km^2,金沙江为1.74×10^6mol/a/km^2,大渡河为1.57×10^6mol/a/km^2,岷江为1.88×10^6mol/a/km^2;流域盆地ФCO2估算结果以大渡河最高为101.81×10^3mol/a/km^2,楚玛尔河最低为7.55×10^3mol/a/km^2,金沙江为44.38×10^3mol/a/km^2,雅砻江为69.64×10^3mol/a/km^2,岷江为81.90×10^3mol/a/km^2,沱沱河为21.90×10^3mol/a/km2^。并对长江流域地表化学剥蚀速率主要控制因素进行了讨论。     

Flotation Separation of Trace Elements from Alkaline-Earth Matrices by Co(III) Hexamethylenedithiocarbamate before ICP-AES Determination

A method for the selective separation of Ag, Cd, Cr, Cu, Ni, Pb and Zn in traces from solutions of calcite (CaCO₃), dolomite (CaMg(CO₃)₂) and gypsum (CaSO₄.2H₂O) before their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) is presented. The expected interferences of Ca and Mg on intensities of trace analytes were removed by collecting the elements of interest with cobalt(III) hexamethylenedithiocar-bamate, Co(HMDTC)₃. The flotation of aqueous solutions (1 l) of calcite, dolomite and gypsum was performed at pH 6.0, by 1.5 mg l⁻¹ Co and 0.6 mmol l⁻¹ HMDTC⁻. To minimise the effect of the reaction between Ca/Mg, which restrains the function of the surfactant, careful selection of the most suitable foaming reagent was necessary. The accuracy of the method was established by analysing natural alkaline-earth minerals by the standard addition method as well as using the dolomite reference materials GBW 07114 and GSJ JDo-1. The ICP-AES limits of detection following flotation on different minerals were found to be 0.080 μg g⁻¹ for Cd, 0.105 μg g⁻¹ for Ag, 0.142 μg g⁻¹ for Cu, 0.195 μg g⁻¹ for Cr, 0.212 μg g⁻¹ for Ni, 0.235 μg g⁻¹ for Zn and 0.450 μg g⁻¹ for Pb.     

A mechanism of shape-transformation of quartz inclusions in albite of regional metamorphic rocks

The process of shape-transformation of quartz inclusions from polyhedral to spherical grains in albite single crystals during metamorphism is mainly controlled by the grain boundary diffusion of oxygen along the quartz/albite interface to reduce the interfacial free energy. The rate of the process, which is represented by the growth rate of the curvature of the edge surface of the grain, depends significantly on temperature and on the grain size of the quartz inclusion. The relations between temperature, T, the time, t_r, and the critical radius, R_c, which is equal to the radius of maximum spherical grains, are given by log R_c = −0.11E_b/RT + 0.25log t_r + C, in which E_b is the activation energy of the grain boundary diffusion of oxygen along the quartz/albite interface and C is a material constant.

The mean critical radius of spherical quartz inclusions in albite is 5 μm for the upper chlorite zone and garnet zone, 10 μm for the lower biotite zone, and 20 μm for the upper biotite zone in the Sambagawa metamorphic terrain. The mean values of the critical radii of spherical quartz inclusions in oligoclase of the Ryoke metamorphic rocks is about 5 μm for the chlorite zone and about 10–20 μm for the sillimanite zone.

Assuming temperatures of about 350°C for the upper chlorite and garnet zones, 400°C for the lower biotite zone, 550°C for the upper biotite zone, and 700°C for the sillimanite zone, the activation energy for the grain boundary diffusion of oxygen along the quartz/plagioclase interfase is estimated to be about 30 kcal/mol.     

季节冻土区公路路基细粒土冻胀敏感性研究

通过4种不同塑性细粒土料的室内闭式冻胀模拟试验,阐述了土的含水量、塑性、饱和度和密实度等因素对冻胀性的影响.在分别建立粘性土和粉土的η~(W-Wp)关系的基础上,综合分析并给出了细粒土的η~(W-Wp)关系.提供了典型土料的η~(W-Wp)~K_d~S_r关系图,提出了细粒土的η~(W-Wp)~K_d/S_r多元线性回归方程式.通过因子贡献率大小分析,指出超塑含水量(W-Wp)大小是影响细粒土冻胀敏感性的主导因素.     

An Ion Chromatography Method for the Determination of Major Anions In Geothermal Water Samples

A single-column suppressed ion chromatography technique was employed for the simultaneous determination of major and trace anions in sulfaterich groundwater samples. An analytical column, a self regenerating suppressor and sodium carbonate as the eluent were used to separate the anions. Method detection limits for the anions of interest were 10.4, 15.9, 36.8, 62, 60, 61 and 67 μg l⁻¹ for F⁻, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, PO₄³⁻ and SO₄²⁻ respectively. The precision of the method was tested at five different concentration levels for each anion reference sample to evaluate the effectiveness of the method for groundwater analysis. Recovery studies were performed between two successive months by adding reference samples to the geothermal groundwater and drinking water samples. Precision was also assessed as the relative standard deviation of both repeatability (within-day) and reproducibility (between-day and different concentrations) for groundwater samples. Standard deviation and RSD values of 220 groundwater samples acquired over 8 months were evaluated. The suppressed ion chromatography technique was found to be a suitable method for determining major anions in sulfate-rich geothermal water samples.     

The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

Determination of Halogens (F, Cl, Br, I), Sulfur and Water in Seventeen Geological Reference Materials

Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l⁻¹. Bromine and I were measured by ICP-MS with detection limits of 1 μg l⁻¹ for Br and 0.1 μg l⁻¹ for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg⁻¹ for F and Cl, 15 mg kg⁻¹ for S, 0.2 mg kg⁻¹ for Br and 0.02 mg kg⁻¹ for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H₂O degassing, reduction on zinc at 1000 °C and H₂ manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.     

Seismic lateral earth pressure coefficients for c–φ soils by slip line method

In this paper, the author proposes a rotation of axes in the solution of slip line equations for determination of lateral earth pressure with the presence of seismic loading under general conditions. A general c–φ soil system under a general condition can be considered so that K_pγ, K_pc, K_pq, K_aγ, K_ac and K_aq can all be determined. For passive pressure, K_pc is found to be much greater than K_pγ and the effect of seismic coefficient on passive pressure is relatively small as compared with the corresponding situation for active pressure. The use of iterative analysis is found to be useful for passive pressure determination but unimportant for active pressure determination.     

Fractal models for the fragmentation of rocks and soils: a review

Fragmentation, the process of breaking apart into fragments, is caused by the propagation of multiple fractures at different length scales. Such fractures can be induced by dynamic crack growth during compressive/tensile loading or by stress waves during impact loading. Fragmentation of rocks occurs in resoonse to tectonic activity, percussive drilling, grinding and blasting. Soil fragmentation is the result of tillage and planting operations. Fractal theory, which deals with the scaling of hierarchical and irregur systems, offers new opportunities for modeling the fragmentation process. This paper reviews the literature on fractal models for the fragmentation of heterogeneous brittle earth materials. Fractal models are available for the fragmentation of: (1) classical aggregate; (2) aggregates with fractal pore space; and (3) aggregates with fractal surfaces. In each case, the aggregates are composed of building blocks of finite size. Structural failure is hierarchical in nature and takes place by multiple fracturing of the aggregated building blocks. The resulting number-size distribution of fragments depends on the probability of failure, P(1/bⁱ) at each level in the hierarchy. Models for both scale-invariant and scale-dependent are reviewed. In the case of scale-invariant P(1/bⁱ)< 1, theory predict: D_f = 3 + log [P(1/bⁱ)]/log[b] for classical aggregates; D_f=D_m+log[P(1/bⁱ)]/log[b] for aggregates with fractal pore space; and D_f=D_s for aggregates with fractal surfaces. where b is a scaling factor and D_f, D_m and D_s are the fragmentation, mass and surface fractal dimensions, respectively. The physical significance of these parameters is discussed, methods of estimating them are reviewed, and topics needing further research are identified.     

高分辨电感耦合等离子体质谱法测定铀矿石样品中234U/238U、230Th/232Th和228Ra/226Ra同位素比值 

采用氢氟酸-硝酸-盐酸混合酸密闭消解含铀矿石样品,用阴离子交换树脂、阳离子交换树脂和锶特效树脂逐级分离富集铀、钍和镭。使用高分辨电感耦合等离子体质谱(HR-ICPMS)测定分离纯化液中234U/238U2、30Th/232Th和228Ra/226Ra同位素。比值的测量精密度取决于比值的大小和对应核素浓度的大小。对质量浓度为10 ng/mL天然铀测量液,234U/238U的测量精密度优于1.2%;对230Th质量浓度为0.6ng/mL且230Th和232Th质量浓度接近的测量液,230Th/232Th的测量精密度为1.2%;对228Ra质量浓度为0.48 pg/mL且228Ra和226Ra质量浓度接近的测量液,228Ra/226Ra的测量精密度为4.0%。     

The (Na–Ca)amphibole–albite–chlorite–epidote–quartz geothermobarometer in the system S–A–F–M–C–N–H2O. 1. An empirical calibration

The proposed geothermobarometer is based on an empirical calibration which takes account of two equilibria involving the tremolite, edenite, pargasite and hastingsite components in amphiboles. It has applications to assemblages found in metabasic rocks of widely different chemical compositions (magnesian to Fe-rich metabasalts), and for metamorphism ranging from lower greenschist to highest amphibolite facies. Knowing the Si_(T1), Al^iv, Al^vi, Fe³⁺, Fe²⁺, Mg, Ca, Na_M4, Na_A and A vacancy in an amphibole, and the Al³⁺ and X _Mg in coexisting epidote and chlorite, it is possible to calculate two values of In K _d for this assemblage. These equilibria involve edenite-tremolite and (pargasite/hastingsite)-tremolite end-members in amphibole (the calculation program is given). For these equilibria, the isopleths (iso-values of K _d) have been calculated for 0.27 < X _Mg < 0.75 and 0 < X _Fe3+= Fe³⁺/(Fe³⁺+ Al^vi) < 0.8. It is then possible to determine pressure and temperature directly when X _Mg, X _Fe3+, In K _d for tremoliteedenite and In K _d for (pargasite/hastingsite)-tremolite are known. Application of this geothermobarometer is limited to Ca-free plagioclase assemblages, and complete P–T paths can be drawn only if all the minerals are considered together. Phase relations at successive stages of crystallization can be constrained by studying the relationships between the coexisting minerals, their zoning and the metamorphic fabrics.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

砂岩铀矿成矿过程与氧化还原分带: 铀系不平衡证据

铀系不平衡技术被用来研究新疆伊犁盆地库捷尔太砂岩型铀矿床的氧化还原分带和成矿过程.取自该矿床的26个样品的铀、钍含量以及234 U/ 238U, 230 Th/ 234 U和230 Th/ 238U活度比值分别用ICP -MS和α能谱仪进行了测量.不同氧化还原带岩石的铀、钍含量和钍/铀比明显不同: 强氧化带岩石的U、Th含量和Th/U比分别为12.4 μg/g, 4.5 μg/g和0.48; 弱氧化带分别为20.4 μg/g, 5.0 μg/g和0.38; 过渡带(矿化带)分别为169.7μg/g, 4.7μg/g和0.07; 还原带(未蚀变带)分别为6.8μg/g, 3.7μg/g和0.87.其同位素特征亦有明显差异: 氧化带岩石234 U/ 238U大多大于1, 过渡带(矿化带)岩石部分大于或等于1, 部分小于1, 还原带(未蚀变带)岩石大多大于1; 氧化带岩石230 Th/ 234 U和230 Th/ 238U大多大于1, 过渡带(矿化带)岩石大多小于或等于1, 还原带(未蚀变带)岩石大多大于1.这可作为砂岩型铀矿床矿体定位的指示剂.铀系不平衡特征还示踪了该矿床的成矿作用过程.      

Determination of Traces of Rare-Earth elements, Yttrium and Thorium in Several International Geological Reference Samples and Comparison Of Data with Other Published Values

Experimental results for most rare-earth elements, yttrium and thorium in several international geological reference samples are presented and compared with other published values, where available. The analytical method used to obtain these results involved a preliminary concentration of the rare-earths On milligram quantities of iron as carrier for atomic-absorption, flame-emission and spectrophotometric determinations, or on milligram quantities of Fe₂O₃, Al₂O₃ and SiO₂ as carriers for optical-emission spectrometric determination.     

植被影响下坡面侵蚀临界水流能量试验研究

坡面侵蚀临界水流能量是反映土壤抗蚀作用强弱的重要特征值.利用人工模拟降雨试验,定量研究了在45mm/h、87 mm/h和127 mm/h降雨强度下、20°陡坡面裸地、草地和灌木地的坡面侵蚀临界水流能量.结果表明,不同植被条件下坡面输沙率随径流切应力、单位水流功率和断面比能的增大而增大,有良好的响应关系.裸地、草地和灌木...     

The Precision of Classical Rock Analysis

Three rock reference samples. W-2, DNC-1, and BIR-1, were analysed five times over several months by classical chemical methods using a Youden Square as the experimental design. A significant variation for the data classified by months was found for SiO₂, CaO, H₂O^-, and TiO₂ among the 15 constituents determined. Nevertheless, most standard deviations for the five data for each oxide in any sample, as well as the error standard deviations from the analyses of variance, are less than or approximately equal to the allowable difference between duplicate determinations traditionally used as limits of error. We also determined nine constituents in three portions each of two samples, W-2 and DNC-1, the six portions being analysed concurrently. F ratios for 16 comparisons of the variances of the five data for an oxide obtained over several months and of the three data determined as a group were significant for only one oxide, total iron as Fe₂O₃ in W-2. We conclude that, if a chemist analyses rock samples carefully, the variation of the determinations will be the same for portions analysed as a group, or analysed over a time interval.     

Significance of Nb/Ta as an indicator of geochemical processes in the crust-mantle system

A mantle value of 17.5 for Nb/Ta appears well established; less well established are crustal values of 11–12, although it appears that Nb/Ta for crustal-derived melts is less than mantle Nb/Ta, demonstrating fractionation of these two elements during crustal evolution, and suggesting that Nb/Ta variation may be indicative of a particular chemical process within the crust-mantle system.

Experimental studies on silicate and carbonatitic liquids at high pressure indicate that, although silicate minerals such as garnet, amphibole and clinopyroxene do fractionate Nb and Ta, the partition coefficients (D's) for both elements are very low. Thus involvement of these minerals may explain relatively small changes in Nb/Ta, but appears inadequate to explain the crust-mantle variation. However, high-quality data for Nb, Ta may be used to provide information on mantle melting or metasomatic processes (e.g., amphibole in the source region decreases Nb/Ta in derived melts, while carbonatitic metasomatism will increase Nb/Ta in affected mantle). Titanate minerals have high D's for Nb and Ta, and do fractionate these elements (e.g., D_Nb/D_Ta rutile/liquid of 0.5–0.8), and their involvement in crystal fractionation would increase Nb/Ta in derivative liquids. In contrast, D_Nb/D_Ta for rutile/fluid is 1.25, so that rocks affected by fluid equilibrated with residual rutile will show a decrease in Nb/Ta

Some Archaean gneisses appear to have high Nb/Ta, and may be a complementary component to that part of the crust which has a relatively low Nb/Ta, such as crustal-derived magmas (e.g., A- ad I-type granites and silicic volcanics). Within the crustal system pegmatites are known to have extremely high and variable Nb, Ta contents, often with low Nb/Ta. A fluid is generally considered to be involved in the generation of these rocks. Thus it is possible that fluid/melt partitioning may be the key to fractionating Nb and Ta, with preference for Ta in the fluid, and enrichment of Ta relative to Nb into the mid-upper crustal system, as the crust evolved, through upward movement of fluid.     

Chemostratigraphy of Neoproterozoic carbonates: implications for 'blind dating'

The δ¹³C_carb and ⁸⁷Sr/⁸⁶Sr secular variations in Neoproteozoic seawater have been used for the purpose of 'isotope stratigraphy' but there are a number of problems that can preclude its routine use. In particular, it cannot be used with confidence for 'blind dating'. The compilation of isotopic data on carbonate rocks reveals a high level of inconsistency between various carbon isotope age curves constructed for Neoproteozoic seawater, caused by a relatively high frequency of both global and local δ¹³C_carb fluctuations combined with few reliable age determinations. Further complication is caused by the unresolved problem as to whether two or four glaciations, and associated negative δ¹³C_carb excursions, can be reliably documented. Carbon isotope stratigraphy cannot be used alone for geological correlation and 'blind dating'. Strontium isotope stratigraphy is a more reliable and precise tool for stratigraphic correlations and indirect age determinations. Combining strontium and carbon isotope stratigraphy, several discrete ages within the 590–544 Myr interval, and two age-groups at 660–610 and 740–690 Myr can be resolved.     

The Use of Multiple Reference Samples for the Monitoring of Ion Microprobe Performance During Zircon 207Pb/206Pb Age Determinations

Data from a series of extended analytical sessions using a range of different zircon reference samples have been used to investigate the periodic derivation of abnormal ²⁰⁷Pb/²⁰⁶Pb ages during microbeam analysis%For the Canberra SHRIMP II, this phenomenon probably results from the presence of a signal at mass 204 that is alien to the Pb spectrum; isotopic fractionation is unlikely to be a significant contributor. In contrast, abnormal ²⁰⁷Pb/²⁰⁶Pb ages obtained from SHRIMP I at the same research centre require a different, but as yet unknown explanation. Assessment of the reasons for atypical ^207Pb/²⁰⁶Pb measurements and the means of correcting for them should therefore be independently assessed for individual analytical instruments. The use of reference samples with very different ages is an effective way of doing this, because older reference samples are more useful for documenting isotopic fractionation, whereas younger ones are more sensitive indicators of isobaric interference.