Donald J. DePaolo

Trace element and isotopic effects of combined wallrock assimilation and fractional crystallization

Equations describing trace element and isotopic evolution in a magma chamber affected simultaneously by fractional crystallization and wallrock assimilation are presented for a model where the mass assimilation rate(Ṁa) is an arbitrary fraction(r) of the fractional crystallization rate(Ṁc). The equations also apply to recharge of a crystallizing magma. Relatively simple analytical expressions are obtained for both radiogenic isotope variations (Nd, Sr, Pb) and stable isotopes (O, H) including the effects of mass-dependent fractionation. Forr = 1 a modified zone refining equation is obtained for trace element concentrations, but forr < 1 behavior is a combination of zone refining and fractional crystallization. Asr → ∞, simple binary mixing is approached. The isotopic and trace element “mixing” trends generated can be much different from binary mixing, especially forr < 1. The model provides the basis for a more general approach to the problem of wallrock assimilation, and shows that binary mixing models are insufficient to rule out crustal assimilation as a cause of some of the isotopic variations observed in igneous rocks, including cases where clustering of isotopic values occurs partway between presumed endmember values. The coupled assimilation-fractional crystallization model provides an explanation for certain trace element and isotopic properties of continental margin orogenic magmas (e.g. Sr concentration versus87Sr/86Sr) which had previously been interpreted as evidence against assimilation. So-called “pseudoisochrons” can be understood as artifacts of contamination using this model. A significant correlation exists between country rock age and low143Nd/144Nd ratios in continental igneous rocks, clearly suggestive that crustal contamination is generally important.

Intercalibration of standards, absolute ages and uncertainties in 40Ar/39Ar dating

The 40Ar/39Ar dating method depends on accurate intercalibration between samples, neutron fluence monitors, and primary 40Ar/40K (or other external) standards. The 40Ar/39Ar age equation may be expressed in terms of intercalibration factors that are simple functions of the relative ages of standards, or equivalently are equal to the ratio of radiogenic to nucleogenic K-derived argon (40Ar/39ArK) values for one standard or unknown relative to another. Intercalibration factors for McClure Mountain hornblende (MMhb-1), GHC-305 biotite, GA-1550 biotite, Taylor Creek sanidine (TCs) and Alder Creek sanidine (ACs), relative to Fish Canyon sanidine (FCs), were derived from 797 analyses involving 11 separate irradiations with well-constrained neutronfluence variations. Values of the intercalibration factors are RFCsMMhb-1 = 21.4876 ± 0.0079; RFCsGA-1550 = 3.5957 ± 0.0038; RFCsTCs = 1.0112 ± 0.0010; RFCsACs = 0.04229 ± 0.00006, based on the mean and standard error of the mean resulting from four or more spatially distinct co-irradiations of FCs with the other standars. Analysis of 35 grains of GHC-305 irradiated in a single irradiation yields RFCsGHC-305 = 3.8367 ± 0.0143. Results at these levels of precision essentially eliminate intercalibration as a significant source of error in 40Ar/39Ar dating. Data for GA-1550 (76 analyses, 5 fluence values), TCs (54 analyses, 4 fluence values), FCs (380 analyses, 40 fluence values) and ACs (86 analyses, 11 fluence values) yield MSWD values showing that the between-grain dispersion of 40Ar∗/39ArK values is consistent with analytical errors alone, whereas MMhb-1 (167 analyses, 4 irradiations) and GHC-305 (34 analyses, 1 fluence value) are heterogeneous and therefore unsuitable as standards for small sample analysis. New K measurements by isotope dilution for two primary standards, GA-1550 biotite (8 analyses averaging 7.626 ± 0.016 wt%) and intralaboratory standard GHC-305 (10 analyses averaging 7.570 ± 0.011 wt%), yield values slightly lower and more consistent than previous data obtained by flame photometry, with resulting 40Ar/40K ages of 98.79 ± 0.96 Ma and 105.6 ± 0.3 Ma for GA-1550 and GHC-305, respectively. Combining these data with the intercalibration approach described herein and using GA-1550 as the primary standard (1.343 × 10−9 mol/g of 40Ar∗; [McDougall, I., Roksandic, Z., 1974. Total fusion 40Ar/39Ar ages using HIFAR reactor. J. Geol. Soc. Aust. 21, 81–89.]) yields ages of 523.1 ± 4.6 Ma for MMhb-1, 105.2 ± 1.1 Ma for GHC-305, 98.79 ± 0.96 Ma for GA-1550, 28.34 ± 0.28 Ma for TCs, 28.02 ± 0.28 for FCs, and 1.194 ± 0.012 Ma for ACs (errors are full external errors, including uncertainty in decay constants). Neglecting error in the decay constants, these ages and uncertainties are: 523.1 ± 2.6 Ma for MMhb-1, 105.2 ± 0.7 Ma for GHC-305, 98.79 ± 0.54 for GA-1550, 28.34 ± 0.16 Ma for TCs, 28.02 ± 0.16 Ma for FCs, and 1.194 ± 0.007 Ma for ACs. Using GHC-305 as the primary standard (1.428 ± 0.004 × 10−9 mol/g of 40Ar∗), ages are 525.1 ± 2.3 Ma for MMhb-1, 105.6 ± 0.3 Ma for GHC-305, 99.17 ± 0.48 Ma for GA-1550, 28.46 ± 0.15 Ma for TCs, 28.15 ± 0.14 Ma for FCs, and 1.199 ± 0.007 Ma for ACs, neglecting decay constant uncertainties. The approach described herein facilitates error propagation that allows for straightforward inclusion of uncertainties in the ages of primary standards and decay constants, without which comparison of 40Ar/39Ar dates with data from independent geochronometers is invalid. Re-examination of 40K decay constants would be fruitful for improved accuracy.

Proterozoic crustal history of the western United States as determined by neodymium isotopic mapping

Initial Nd isotopic ratios of crystalline rocks from an area of ∼ 1.5 × 10 6 km 2 of the western United States have been determined in order to map Precambrian age province boundaries and thus document the growth and modification of the North American continent in the Proterozoic. The use of three representative rock suites of different ages— Mesozoic and Tertiary peraluminous granitic rocks, middle Proterozoic (ca. 1.4 Ga) “an-orogenic” granitic rocks, and lower Proterozoic (ca. 1.7 Ga) igneous and metamorphic rocks—allows the ages of the provinces to be distinguished on the basis of different Nd isotopic evolution paths rather than solely on the basis of model ages. Three age provinces have been delineated, each generally northeast-southwest trending, having decreasing crystallization ages and increasing initial e Nd values with increasing distance southeastward from the Archean craton. Province 1 is composed of crustal rocks of central Utah and northeastern Nevada, which are characterized by average values of e Nd (1.7 Ga) ≈ 0 and T DM ≈ 2.0–2.3 Ga. Province 2 covers Colorado, southern Utah, and northwestern Arizona and has e Nd (1.7 Ga) ≈ +3 and T DM ≈ 1.8–2.0 Ga. Province 3, which comprises the basement rocks of New Mexico and southern Arizona, has e Nd (1.7 Ga) ≈ +5 and T DM ≈ 1.7–1.8 Ga. An additional region of province 1-type isotopic characteristics, herein named “Mojavia,” is found in eastern California and western Nevada. Crust formation in each province involved a large component of mantle-derived material plus a moderate amount (∼20%) of pre-existing crust. As the new crust was built outward from the Archean nucleus, however, contributions of Archean material to the newly forming crust were more effectively screened, so that the most distal province (3) is derived almost entirely from Proterozoic mantle. The province boundaries are subparallel to the crystallization age trends determined by other workers. An exception to this is the Mojavia region of province 1, which crosscuts and truncates the other provinces in the region of the lower Colorado River. This region appears to be displaced relative to other areas of the North American basement that have similar isotopic characteristics. This suggests the presence of a previously unrecognized large-scale, left-lateral, north-south–trending basement offset of Proterozoic age in the vicinity of the California-Arizona border.

Rapid production of continental crust 1.7 to 1.9 b.y. ago: Nd isotopic evidence from the basement of the North American mid-continent

Nd isotopic analyses of Precambrian granitic rocks from the central United States were made to determine crust-formation ages and thereby to investigate the structure and evolution of central North America. Samples of anorogenic granites that have 1.4-b.y. crystallization ages yield model TDM ages of 1.77 to 1.98 b.y. that indicate a previously undocumented 0.4- to 0.6-b.y.-old precrystallization crustal history. These and previously published data approximately define the boundaries of a large segment of continental crust that was formed from the mantle during a relatively short interval ∼1.9 b.y. ago. Both 1.4- and 1.8-b.y.-old samples from the Penokean terrene of central Wisconsin yield distinctly older TDM model ages of 2.1 to 2.3 b.y. Approximately 1.1-b.y.-old samples from the Llano uplift in Texas yield crust-formation ages of 1.3 to 1.4 b.y. The data appear to delineate provinces with well-defined, nonoverlapping crust-formation ages that young to the south, indicating episodic formation of the North American continental crust during Proterozoic time. The initial 143Nd/144Nd ratios of the 1.4-b.y.-old granites are varied ( ϵ Nd = +4.8 to −2.0). Most of the samples analyzed probably represent crustal melts, but the existence of some high initial ϵ Nd values indicates an admixture of mantle-derived material. The isotopic patterns suggest that the 1.4-b.y.-old “anorogenic” plutonism may be an inland manifestation of subduction activity related to formation of Llano crust. The data also indicate that the Penokean terrane is not entirely 1.8-b.y.-old, mantle-derived material, nor simply reworked Archean crust. It may represent a mixture of Archean and juvenile mantle material added during the 1.84 Ga Penokean orogeny. Patterns of continental growth deduced from this study emphasize the episodicity of crust formation. Construction of an apparent crustal growth curve for North America indicates that the average age of the continent is ∼2.2 b.y., which is significantly older than the average age of ∼ 1.5 b.y. derived from Rb-Sr studies.

High-resolution stratigraphy with strontium isotopes

The isotopic ratio of strontium-87 to strontium-86 shows no detectable variation in present-day ocean water but changes slowly over millions of years. The strontium contained in carbonate shells of marine organisms records the ratio of strontium-87 to strontium-86 of the oceans at the time that the shells form. Sedimentary rocks composed of accumulated fossil carbonate shells can be dated and correlated with the use of high precision measurements of the ratio of strontium-87 to strontium-86 with a resolution that is similar to that of other techniques used in age correlation. This method may prove valuable for many geological, paleontological, paleooceanographic, and geochemical problems.

Sr isotope evolution of seawater: the role of tectonics

We use a high-resolution seawater Sr isotopic evolution curve for the last 100 m.y. in conjunction with modern riverine Sr flux measurements, and also geologic, tectonic and geochronological data, to make the case for a close relationship between seawater Sr isotopic composition and the India Asia continental collision. Using a simple seawater Sr budget model we begin by showing that the Sr flux associated with alteration of seafloor basalts is too small and does not have the right time evolution to account for much of the seawater Sr isotopic curve of the last 100 m.y. The flux of dissolved Sr carried by rivers originating in the Himalaya-Tibet region on the other hand is presently a significant fraction of the global Sr budget. We calculate how this riverine flux would have had to change with time in order to match the observed seawater Sr isotopic curve and find that the riverine flux remains relatively constant prior to the collision of India with Asia but then increases very significantly after collision. We note that the period of most rapid change in seawater Sr isotopic ratio, from 20 Ma to 15 Ma, is also a period of exceptionally high erosion in parts of the Himalayas and the Tibetan Plateau. As further evidence that Sr derived from the collision of India with Asia plays a major role in the Sr isotopic evolution of seawater we show that the total amount erosion of the Himalaya-Tibetan Plateau since collision, which we calculate separately, represents a total amount of Sr that is very nearly the same as the cumulative amount required by the Sr isotopic change of seawater since collision. The relationship between erosion and riverine Sr flux allows us to use the Sr isotopic evolution of seawater to reconstruct a history of erosion since collision, and we find that the erosion rate accelerates with time since collision, with the present having the largest rate. When we apply the Sr budget model to the entire Phanerozoic using a new compilation of deformed continental area versus time we find that we can account for the large-scale structure of the seawater Sr isotopic curve, but fail to reproduce several local maxima and minima, especially in the period 100-300 Ma. The present high S7Sr/S6Sr of seawater and similar highs in the Devonian and Cambrian do correlate with extensive deformation on the continents.

Isotope fractionation by chemical diffusion between molten basalt and rhyolite

Abstract Experimental diffusion couples were used to study chemical diffusion between molten rhyolite and basalt with special emphasis on the associated fractionation of calcium and lithium isotopes. Diffusion couples were made by juxtaposing firmly packed powders of a natural basalt (SUNY MORB) and a natural rhyolite (Lake County Obsidian) and then annealing them in a piston cylinder apparatus for times ranging from 0.1 to 15.7 h, temperatures of 1350–1450°C, and pressures of 1.2–1.3 GPa. Profiles of the major elements and many trace elements were measured on the recovered quenched glasses. The diffusivities of all elements except lithium were found to be remarkably similar, while the diffusivity of lithium was two to three orders of magnitude larger than that of any of the other elements measured. Chemical diffusion of calcium from molten basalt into rhyolite was driven by a concentration ratio of ∼18 and produced a fractionation of 44Ca from 40Ca of about 6 ‰. Because of the relatively low concentration of lithium in the natural starting materials a small amount of spodumene (LiAlSi2O6) was added to the basalt in order to increase the concentration difference between basalt and rhyolite, which was expected to increase the magnitude of diffusive isotopic fractionation of lithium. The concentration ratio between Li-doped basalt and natural rhyolite was ∼15 and the resulting diffusion of lithium into the rhyolite fractionated 7Li from 6Li by about 40‰. We anticipate that several other major rock-forming elements such as magnesium, iron and potassium will also exhibit similarly larger isotopic fractionation whenever they diffuse between natural melts with sufficiently large differences in the abundance of these elements.

Petrogenetic mixing models and Nd-Sr isotopic patterns

The possible Nd and Sr isotopic variations which would result from assimilation of continental crust by mantle-derived magmas can be systematized by considering the chemical and isotopic compositions of the magmas and models for layering within the continental crust. These systematics may provide a valuable framework for studying crustal contamination, the formation of magmas within the crust, and the chemical and age structure of continental segments. The isotopic patterns arise from (1) the overall contrast in Nd and Sr isotopic composition between old continental crust and mantle magma sources, (2) regularities in the variations of ^(143)Nd/^(144)Nd and ^(87)Sr/^(86)Sr in crustal rocks which are related to age and the contrasting geochemical behavior of Sm and Nd relative to Rb and Sr. Consideration of two-component mixing models suggests that the correlation of initial Nd and Sr isotopes in selected young basalts could represent a mixing line, possibly between mantle reservoirs of distinct chemistry and age. However, the possibility that the trend results from mixing of old low - Sm/Nd, high - Rb/Sr crustal material with complementary high - Sm/Nd, low - Rb/Sr mantle reservoirs cannot be eliminated. Such recycling of crust into the mantle could occur in subduction zones. One problem with a recycling model to explain the correlation is that it requires the crustal endmember to have chemical and isotopic properties which do not appear to be common in crustal rocks.

Reconstructing past sea surface temperatures: Correcting for diagenesis of bulk marine carbonate

A numerical model which describes oxygen isotope exchange during burial and recrystallization of deep-sea carbonate is used to obtain information on how sea surface temperatures have varied in the past by correcting measured δ18O values of bulk carbonate for diagenetic overprinting. Comparison of bulk carbonate and planktonic foraminiferal δ18O records from ODP site 677A indicates that the oxygen isotopic composition of bulk carbonate does reflect changes in sea surface temperature and δ18O. At ODP Site 690, we calculate that diagenetic effects are small, and that both bulk carbonate and planktonic foraminiferal δ18O records accurately reflect Paleogene warming of high latitude surface oceans, biased from diagenesis by no more than 1°C. The same is likely to be true for other high latitude sites where sedimentation rates are low. At DSDP sites 516 and 525, the effects of diagenesis are more significant. Measured δ18O values of Eocene bulk carbonates are more than 2% lower at deeply buried site 516 than at site 525, consistent with the model prediction that the effects of diagenesis should be proportional to sedimentation rate. Model-corrections reconcile the differences in the data between the two sites; the resulting paleotemperature reconstruction indicates a 4°C cooling of mid-latitude surface oceans since the Eocene. At low latitudes, the contrast in temperature between the ocean surface and bottom makes the carbonate δ180 values particularly sensitive to diagenetic effects; most of the observed variations in measured δ18O values are accounted for by diagenetic effects rather than by sea surface temperature variations. We show that the data are consistent with constant equatorial sea surface temperatures through most of the Cenozoic, with the possible exception of the early Eocene, when slightly higher temperatures are indicated. We suggest that the lower equatorial sea surface temperatures for the Eocene and Oligocene reported in other oxygen isotope studies are artifacts of diagenetic recrystallization, and that it is impossible to reconstruct accurately equatorial sea surface temperatures without explicitly accounting for diagenetic overprinting.

Crustal growth and mantle evolution: inferences from models of element transport and Nd and Sr isotopes

Abstract Transport equations describing relative radiogenic isotope evolution for long-lived radioactive elements ( λ −1 ⪢ age of the earth) are derived for a model of continental crust extraction from a uniform depleting mantle with crustal recycling. The equations are integrated for arbitrary crustal growth histories with easily evaluated solutions obtained for cases involving 1. (i) no return of crust to the mantle, 2. (ii) small amounts of crust continuously returned to the mantle, 3. (iii) a steady-state crust. Application of the model to Sm-Nd and Rb-Sr isotopic evolution shows that the deviations—ϵ Nd and ϵ Sr —from an unfractionated reference reservoir are primarily dependent upon the relative masses of crust and mantle, and the mean age of the crust 〈 T 〉 c . For plausible values of 〈 T 〉 c , the isotopic compositions of modern oceanic basalts indicate that only about 25–50% of the mantle is needed to balance the crust. The calculations quantify the non-uniform depletion of the mantle previously inferred from trace-element studies and suggest that mantle of the type represented isotopically by mid-ocean ridge basalts must comprise only a small fraction of the whole mantle. Published data on initial 143 Nd 144 Nd in ancient and modern crustal rocks are compatible with models of secular growth of the continental crust with zero or small amounts of recycling of crust over the past 3.6 AE. The data do not support a steady-state model for the crust. Data on Archaean rocks suggest either the total absence of crust older than about 3.6 AE or very rapid crustal cycling from 4.55 to 3.6 AE ago. The transport parameters for Rb and Sr are deducible from those of Sm and Nd, which can be estimated more accurately, by consideration of the Nd-Sr isotopic correlation in oceanic basalts and indicate that the upper mantle may be depleted of up to 90% of its Rb, suggesting similar depletion factors for K, U, Th. Recycling of crustal Sr via transfer of 87 Sr from ocean water to oceanic crust during hydrothermal alteration may be significant but is insufficient to seriously affect interpretation of the Nd-Sr isotopic correlation.