The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR‐1, 2; BHVO‐1, 2), andesite (AGV‐1, 2), rhyolite (RGM‐1, 2), syenite (STM‐1, 2), granodiorite (GSP‐2), and granite (G‐2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR‐1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC‐ICP‐MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR‐ICP‐MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC‐ICP‐MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC‐ICP‐MS, respectively). Our results also show that the first‐ and second‐generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC‐ICP‐MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC‐ICP‐MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first‐ and second‐generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

The present work reports multiple collector inductively coupled plasma mass spectrometry (MC‐ICP‐MS) measurements of the isotopic compositions of Hf and Pb in the first 3 km of the deep core retrieved by the Hawaii Scientific Drilling Project. The measurements cover all the samples from the standard geochemical reference set, glasses from the deep hole, and replicates from the pilot hole. Both Hf and Pb are less radiogenic in Mauna Loa compared to Mauna Kea. The transition between Mauna Kea and Mauna Loa lavas in the deep core is progressive for εHf and 208Pb/204Pb, but a sharp discontinuity is observed for 208Pb*/206Pb*. There is no correlation between the alkalinity of the samples and isotopic composition. In detail, the Hf isotope compositions of samples from the pilot hole are not all identical to those of the HSDP‐2 core for samples retrieved from a similar depth, suggesting that steep topography existed at the time of emplacement or that a different eruptive sequence was recorded. The strong correlation between 208Pb*/206Pb* and 3He/4He (He data from M. D. Kurz et al. (Rapid helium isotopic variability in Mauna Kea shield lavas from the Hawaiian Scientific Drilling Project, submitted to Geochemistry Geophysics Geosystems, 2002)) requires the episodic incorporation of a component that resembles the basalts erupted by either Kilauea or the Loihi eruptive centers (this component is referred to as K/L). The data suggest that some 500 kyr ago, Mauna Kea was tapping a mantle source similar to that tapped by Kilauea today. Isotopic variability of Pb and He cannot be accounted for by radiogenic ingrowth in a closed system, but requires the mixing of mantle source components with distinct outgassing histories. The time series of isotopic and concentration data in Mauna Kea samples spanning about 350,000 years of age indicate the recurrence of geochemical patterns in the melting column. Ignoring the most recent alkalic samples, we find that the dominant fluctuations of εHf and 207Pb/204Pb correspond to a period of 50,000 years. For La/Yb, Zr/Nb, 87Sr/86Sr, 206Pb/204Pb, 207Pb/206Pb, and 208Pb/206Pb, a dominant period of ca. 18,000 years is obtained. Once provision is made for the existence of harmonics, the consistency between the isotopic spectrum of the pilot hole and the HDSP‐2 core is very good. The input of the K/L component does not seem to be periodic. We use these recurrence intervals in conjunction with the upwelling rate deduced from buoyancy flux and seismic evidence of the maximum dimension of scatterers to constrain the radius of the Hawaiian plume conduit to be in the range of 10–50 km and the upwelling velocity to be in the range of 0.13–3 m/yr. Plausible vertical length scales of heterogeneities in the conduit are 6.5–160 km.

. Reproducibility is better than 50 ppm for the granitoid compositions and better than 40 ppm for the basaltic/andesitic compositions. For the isotopic analyses acquired early in this project on glass columns, Hf isotopic analyses from several of the reference materials were significantly less reproducible than Nd and Sr isotopic analyses determined from the same sample dissolution. The 176 Hf/ 177 Hf ratios for relatively radiogenic compositions (BCR-1, 2; BHVO-1, 2; RGM-1) were shifted systematically toward lower values by 100-150 ppm when a borosilicate primary column was used. Although systematic, the shift for felsic compositions was generally within analytical error, except for GSP-2, which has a very low Hf isotopic ratio, where the shift was to higher Hf and high Hf concentrations of the borosilicate glass column (16 ppm) and frit material (22 ppm) indicate that only small amounts of such unradiogenic material could cause significant contamination of small samples. For the basaltic (BCR-1, 2; BHVO-1, 2) and rhyolitic (RGM-1) samples, approximately 3 ng of Hf from the column or frit would be enough to produce the observed 100-150 ppm shift. Accurate, high-precision 176 Hf/ 177 Hf data can only be acquired if samples are processed using all PTFE Teflon 1 labware, or quartz and polypropylene.

[1] The recent development of multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) and increasing use of the technique have created the need for well-characterized rock standards, especially for isotopic systems where no internal fractionation correction can be applied. This paper presents a careful leaching experiment on the U.S. Geological Survey (USGS) reference materials BHVO-1 and BHVO-2 (Hawaiian basalts) and documents the evidence for contamination of the rock powders during processing. This contamination accounts for the difference in Pb isotopic ratios of BHVO-1 and BHVO-2 as well as for their lack of homogeneity both in Pb isotopic compositions and in some trace element contents.

No abstract