Normalizing to the VPDB standard, the delta values for glacial and interglacial forams are (-0.203) and (-1.809) per mil.

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1 Problem Set #3 Solutions Question 1.1 An ion current of ampere (A = C s -1 ; Ampere = Coulomb per second) corresponds to 6,415,096 elementary charges arriving at the detector per second, taking the elementary charge of e = C into account. Assuming identical transmission between SEM and Faraday detectors, the ratios of the 18 O and 16 O ion beams are: for glacial forams and for interglacial forams. Question (5 points) Normalizing to the VPDB standard, the delta values for glacial and interglacial forams are -0.0 (-0.03) and (-1.809) per mil. The saturated mixing ratio at 0 C air temperature and 1000 mbar is gram per kilogram. The saturated mixing ratios at -5 C and - C at the same pressure and starting temperatures (assuming saturation) are.63 grams/kg and 0.65 grams/kg. This means that the water vapor fractions remaining for both scenarios are (0.177) (0.044), respectively (calculated using the Mixing atio calculator at Question 1.1. (5 points) Note that the universal gas constant needs to be in units of cal mol -1 K -1 (i.e ), and that the temperature values (in degree Celsius) need to be converted to Kelvin. The alpha values for the relevant temperatures are: 0 C C (this is the mean temperature of 0 C and -5 C) -1 C (this is the mean temperature of 0 C and - C) -5 C C , indicating greater fractionation at lower temperatures. Question (5 points) Calculate delta values for the condensate from Willi Dansgaard s formula #6 in his 1964 Tellus (4, ) article. These values (relative to SMOW) are: ( ) per mil for the Emiliani (cooling from 0 C to -5 C) case and ( ) per mil for the Dansgaard & Tauber (cooling from 0 C to - C) case. These values are the values of ice locked in the 130 meters of ice-equivalent water that melted since the last glacial maximum. The 69 meters of water-equivalent ice existing during the current interglacial is 5 per mil heavier, i.e per mil for the Emiliani case

2 -5.4 per mil for the Dansgaard & Tauber case. Question 1. (0 points) Charette and Smith (010, The Volume of Earth s Ocean, Oceanography 3, No. ) have determined the volume of the ocean at km 3 (area: km, mean depth: 368. m). Neglecting changes in density, thermal expansion, topography and changes in the area of the ocean on G-IG time scales, 130 meter water-equivalent ice has a volume of km 3, whereas the remaining 69 meters of water-equivalent ice correspond to a volume of km 3. The remaining (IG) ice is 5 per mil heavier than the corresponding glacial ice. The simple mass balance is then: Emiliani: Dansgaard & Tauber: 18 O sw = 18 O sw = = 0.66 per mil = 1.1 per mil With a total change of 1.61 per mil, Emiliani s scenario attributes 41 (40.99) % to changes in ice volume and composition, whereas Dansgaard & Tauber argue that it is 75 (75.16) %. Question 1.3 (0 points) The Erez & Luz (1983, best-fit constants below are from their table ) equation for paleotemperature (in C) is: T ( C) = ( 18 O carb 18 O sw ) ( 18 O carb 18 O sw ) Note that this equation requires delta values normalized to VPDB, not VSMOW. The equation also relies on measurements of CO released from carbonates upon decomposition with phosphoric acid ( 18 O carb ), and on equilibrating CO with seawater ( 18 O sw ) at a constant temperature ( 18 O of seawater is very difficult to measure directly, because water is such a sticky molecule in mass spectrometers). The 18 O sw term in the equation (relative to VPDB) can be related to our VSMOW scale by: 18 O sw-vpdb = 18 O sw-vsmow 0.7 The relevant differences (parentheses) in the Erez & Luz equation are therefore: Interglacial: ( 18 O carb 18 O sw ) = Emiliani glacial: ( 18 O carb 18 O sw ) = Dansgaard & Tauber glacial: ( 18 O carb 18 O sw ) = With this, the interglacial temperature is 4.0 C. The glacial temperature with the Emiliani scenario is C, whereas the glacial temperature with the Dansgaard & Tauber scenario is.0 C. The glacial-interglacial temperature differences derived for these two scenarios are 4.3 C (Emiliani) and 1.8 C (Dansgaard & Tauber).

3 Note: the above conversion deal with measurements of CO gas (real life, CO measurements generated by reacting carbonate with phosphoric acid, or by equilibrating CO gas with seawater at 5 C in socalled Kiel devices originally developed at GEOMA in Kiel, Germany), as our foram data were generated in this fashion. If you want to convert delta values from VPDB to VSMOW scales or vice versa, the following equations have to be used (the numbers in parentheses are alternative values different conversion schemes have slightly different constants (i.e (9) means that one study uses a value of whereas another uses a value of ), giving you a sense of the uncertainty associated with these conversions: 18 O VSMOW = (9) 18 O VPDB (30.9) 18 O VPDB = (01) 18 O VSMOW 9.94 (9.9)

4 Question (15 points) We start by realizing that the measurement will be limited by the count-rate of the less abundant isotope. This is C 18 O 16 O, which is 0.4% of the more abundant C 16 O 16 O. Put another way, the 16 O count will be 50 times greater than the 18 O count, and hence measured to 16 times greater accuracy. Considering the implied imprecision of the other factors given and the way errors propagate in the isotope ratio calculation, ignoring this contribution to measurement error is justified. Now since the measurement is ion current limited, and the target precision is 0.01 (one part in 10 5 ), it would at first seem that we would need to acquire counts (recall that counting precision goes as N -0.5 ). However, since we need to measure both unknown and standard, we need to now both better due to the propagation of errors. That is, we need to have a precision that is 1 better for both. (Think about computing the ratio of the two and propagating the errors!) Thus we need to count twice as many ions for both standard and unknown. Inasmuch as the standard will likely be unlimited in size and we re asked to determine how much unknown we need, we proceed with that. Working backwards from that, there will be approximately 50 ions delivered to the detectors for every one C 18 O 16 O ion received. Thus we need to deliver 50 x x = 5 x 10 1 CO + ions (remember the factor of two because of the standard/unknown symmetry. Now we need to feed the source 900 atoms for every ion sent to the detectors, so the requirement now becomes 4.5 x CO molecules. Finally, the gas delivery system is only 50% efficient so we need to have 9 x CO molecules in our sample. Given Avogadro s number, this means that we require atoms 8 S mole 0.015mol atoms mole Now the over-fastidious student might consider the contribution of C 13 O 16 O 17 and C 1 O 17 O 17 to the mass 46 channel. The presence of other ions, that can and would be subtracted, will pollute the ion counts and inflate the error. Fortunately, the contributions (an exercise to the student) are extremely small.

5 Question 3 (15 points) The first step is to list the isotopologues of N O, and then give the normalized ion currents, given by isotope ratios relative to the most abundant isotopes: Mass Isotopologues atios N 14 N 16 O = N 14 N 16 O + 14 N 15 N 16 O + 14 N 14 N 17 O * 15/ / N 15 N 16 O + 14 N 15 N 17 O + 15 N 14 N 17 O + 14 N 14 N 18 O 15/14 + * 15/14 * 17/ /16 Substituting the atmospheric isotopic ratios for 15 N/ 14 N = x 10-3, 17 / 16 O = x 10-4, and 18 O/ 16 O =.005 x 10-3, we can substitute into the istopologue list above to get 45/44 = x 10-3 and 46/44 =.0151 x 10-3 for the N O distributions. This is what we actually measured. We then do the same for the CO distributions, which have a slightly greater number (5) of isotopologues at mass 46, we create the following equations: 45/44 = 13/1 + * 17/16 = x /44 = * 13/1 17/16 + * 18/ /16 =.005 x 10-3 This is two equations in three unknowns, so we need to use a third constraint to solve for all three variables, which is that since δ 17 O = δ 18 O. Substituting into the definition of δ referenced to SMOW, we have 17/16 18/16 Unknown Unknown /16 SMOW 18/16 SMOW And substituting in the values for SMOW, this reduces to /16 Unknown 18/16 Unknown Now we have three equations in three unknowns, which can be solved either iteratively (the hard way), by substitution of the third equation into the first two combined with a little algebra, or with a non-linear equation solver (e.g., in MATLAB). We get 13 13/ PDBC / O 496 You could also solve the above problem using 45/44 and 46/45, but it would be more complicated. SMOW

6 Question 4 (15 points) I preface this solution with an apology: Kyrstin pointed out an error in the G units used (they were listed as kj/mol) in the table, but they should be in the older units of kcal/mol. This means that those who did not receive correct guidance on the error were off by a factor of ~e 4, or an order of magnitude. Students were not penalized for this, although I need a good flogging. We first write out the reaction equation: H +HDO HD+HO which allows us to write the reaction constant as G H HO HD T K e HO HDOH where the un-subscripted is the gas constant (not to be confused with the isotope ratios). We can rewrite this as G HO T e H Now we can calculate from the table values that G G f HDG f H OG f H G f HDO kcal mol Substituting the value for T Cal kcal T K mol K mol we get ln e Since the original gas has δd= -60 with respect to VSMOW, it s ratio is (remember you should always convert to and work in terms of isotope ratios, and then compute delta values). This means the final ratio of the water vapor with respect to VSMOW is x = 3.56 (note that this is a huge effect, while typical values for other isotopes are much closer to unity). That is, there is a strong affinity for D to concentrate preferentially in the water molecule. Using the delta notation, we arrive at D HO = 56 If you write the original equation in reverse, i.e., HD+HO H +HDO it still works out the same because the different summation/difference would lead to the sign in the exponent for α being the opposite and we would have to use 1/α to have the correct sense. That is, the equations have symmetry.