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Laboratory

Water - δ17O, δ18O, Δ17O

Overview

We employ the water fluorination method using Cobalt (III) fluoride to convert H2O into O2 for subsequent triple oxygen isotope analysis on a Thermo MAT253. Water is fluorinated to produce O2 as previously described (Barkan and Luz 2005, Baker et al. 2002, Barkan and Luz 2007) and the O2 is collected as in Abe (2008). Briefly, 2 mL of water was injected into a 370 °C 15 cm long nickel column containing 7 g CoF3 converting H2O into O2 and creating HF and CoF2 as byproducts. Helium carried O2 at 30 mL min-1 through a trap submerged in liquid nitrogen to collect HF, which is later vented to a fume hood; the NaF trap originally recommended by Baker et al. (2002) is not used. The O2 sample is collected in a trap for 20 min, and then transferred to a 14 cm stainless steel cold finger. Both the trap and cold finger contained approximately 40 mg of 5A (4.2 to 4.4 Å) molecular sieve and were submerged in liquid nitrogen. To minimize memory effects, following Barkan and Luz (2005) we injected and discarded a minimum of four injections when switching between waters with a difference in δ18O value of greater than 5 permil. The cold fingers are sealed using a bellows valve.

The O2 samples are warmed to 60 °C and expanded for 10 min into the sample bellows through a custom multiport on a dual-inlet ThermoFinnigan MAT 253 isotope ratio mass spectrometer (Thermo Electron, Bremen, Germany) with Faraday cup amplifiers for m/z 32, 33, and 34 of 1*109 Ω, 1*1012 Ω, and 1*1011 Ω, respectively. The custom designed multiport used air-actuated bellows valves, air pressure control originally intended for a stock microvolume, and modified ISL scripts. The O2 sample was analyzed for m/z 32, 33, and 34 abundance ratios to determine d18O and d17O values with reference to O2 gas (δ17O measured s/VSMOW=-4.319 permil, δ18O measured s/VSMOW=-8.255 permil). Each mass spectrometric measurement comprised 90 sample-to-reference comparisons. Each of these comparisons consisted of 26 s of integration and 15 s of idle time. After every 30 comparisons, the m/z 32 signals of the sample and reference gases were balanced to 10 V and the mass spectrometer was peak-centered on m/z 33. The reference bellows was automatically refilled before each sample to a pressure that was equal to that of the sample. Over the course of these measurements the mass spectrometer exhibited an internal reproducibility of 0.002 permil, 0.004 permil, and 0.0037 permil (3.7 per meg) for δ17O, δ18O, and 17Oexcess values, respectively. We use VSMOW, SLAP, and GISP to calibrate our water fluorination system. We have also measured select in-house reference waters for 17Oexcess17O).

Sample submission

We accept samples for water Δ17O analysis on a collaborative basis. The first step, then, is for you to tell us about the goals and purpose of the measurements. If needed, we will work with you to design an appropriate analysis strategy. You can choose to visit IsoLab and perform analyses yourself, or we can analyze the samples for you. We will then work together when interpreting the data. We would discuss the plan at length and make sure the data make sense for you to interpret. We are not able to do “contract” work (i.e., analyze samples without knowing what they are or taking part in the interpretation) because the method is so time consuming, and it is new enough that issues of standardization and calibration make it important to work out with an expert on a case-by-case basis. But as long as it involves scientific collaboration and we get to do quality control on the final dataset, we welcome visitors and/or samples. We typically schedule analyses ~3-6 months in advance.

To calculate costs start with our rates page. This method requires only the Water - Δ17O for both preparation and analysis. These rates are per analysis not per sample and we require at least triplicates for a sound interpretation (# of samples x # replicates = total analyses). If you send someone here to learn the method and do the analyses, the cost is calculated using the "Off Campus Funding, Lab Provided Labor" lane until the visitor is independent in analysis and data reduction (three days seems to be the minimum) then the "Off Campus Funding, User Provided Labor" for every day after that. If we run your samples for you, use the "Off Campus Funding, Lab Provided Labor" lane.

We prefer a minimum of 5 mL of sample in a labeled, water-tight, plastic or glass container with simple legible sample IDs. We need to know if it is fresh or salt water.

Standard Operating Procedures

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