Precise Sector Field ICP-MS Small Foraminiferal Sample Multi-Elemental Ratios ----------------------------------------------------------------------- World Data Center for Paleoclimatology, Boulder and NOAA Paleoclimatology Program ----------------------------------------------------------------------- NOTE: PLEASE CITE CONTRIBUTORS WHEN USING THIS DATA!!!!! NAME OF DATA SET: Precise Sector Field ICP-MS Small Foraminiferal Sample Multi-Elemental Ratios LAST UPDATE: 1/2007 (Original receipt by WDC Paleo) CONTRIBUTOR: Tom Marchitto, University of Colorado IGBP PAGES/WDCA CONTRIBUTION SERIES NUMBER: 2007-003 SUGGESTED DATA CITATION: Marchitto, T.M. 2007. Precise Sector Field ICP-MS Small Foraminiferal Sample Multi-Elemental Ratios. IGBP PAGES/World Data Center for Paleoclimatology Data Contribution Series # 2007-003. NOAA/NCDC Paleoclimatology Program, Boulder CO, USA. ORIGINAL REFERENCE: Marchitto, T.M. 2007. Precise multielemental ratios in small foraminiferal samples determined by sector field ICP-MS. Geochem. Geophys. Geosyst., 7, Q05P13, doi:10.1029/2005GC001018. ABSTRACT: Inductively coupled plasma mass spectrometry (ICP-MS) holds two main advantages over other techniques for the measurement of foraminiferal elemental ratios: (1) numerous trace metals may be precisely and simultaneously measured, and (2) smaller samples may theoretically be used. Methods are presented for the precise determination of Mg/Ca, Sr/Ca, Cd/Ca, Zn/Ca, Li/Ca, U/Ca, Mn/Ca, and Fe/Ca by sector field ICP-MS. Analytical precision is largely independent of sample size over the range of ~5 to 125 ug CaCO3, eliminating the need for narrow target dilutions. Long-term 1 sigma precisions are as follows: Mg/Ca = 0.54%, Sr/Ca = 0.57%, Cd/Ca = 1.8%, Zn/Ca = 3.2%, Li/Ca = 0.88%, U/Ca = 1.9%, Mn/Ca = 0.97%, and Fe/Ca = 1.4%. For Mg/Ca, actual foraminiferal samples appear to give reliable results below 10 ug CaCO3 (postcleaning mass). GEOGRAPHIC REGION: N/A PERIOD OF RECORD: N/A FUNDING SOURCE: INSTAAR, University of Colorado, and US National Science Foundation (OCE-0214221, OCE-0221979, OCE-0425522) DESCRIPTION: 46Ca/43Ca count ratios were blank-corrected and normalized to bring mean of standards in each run to 2.6. Metal/Ca deviations were calculated as (Me/Ca)meas/(Me/Ca)known - 1. Outliers are 2s relative to linear equations through all data. Final sample masses were calculated from measured [Ca]. VARIABLES AND UNITS: 46Ca/43Ca count ratios (%) Ca concentrations (mM) Metal/Ca deviations from known (ratio-1) G. bulloides Mg/Ca (mmol/mol) sample size as mass CaCO3 (ug) PRECISION: Mg/Ca: 0.54% Sr/Ca: 0.57% Cd/Ca: 1.8% Zn/Ca: 3.2% Li/Ca: 0.88% U/Ca: 1.9% Mn/Ca: 0.97% DATA: 1a. Fig. 2, Ti interference Part 1 of 2: 8/23/04, 10/2/04, 12/3/04, 8/28/04, 12/8/04 8/23/04 8/23/04 10/2/04 10/2/04 s 12/3/04 12/3/04 8/28/04 8/28/04 8/28/04 12/8/04 12/8/04 12/8/04 12/8/04 46/43Ca stds[Ca] 46/43Ca stds[Ca] 46/43Ca stds[Ca] 46/43Ca stds[Ca] PC14[Ca] 46/43Ca stds[Ca] PC14[Ca] MAR[Ca] 2.5706 2.0060 2.6016 2.0060 2.6166 2.0060 2.6260 2.0060 2.6176 2.0060 2.5867 2.0333 2.6057 2.0333 2.6068 2.0333 2.5865 2.0333 2.6089 2.0333 2.5736 2.0269 2.6084 2.0269 2.6043 2.0269 2.5981 2.0269 2.5997 2.0269 2.5966 2.0393 2.5837 2.0393 2.5981 2.0393 2.5762 2.0393 2.5688 2.0393 2.5464 2.0089 2.5894 2.0089 2.5837 2.0089 2.6712 2.0089 2.5790 2.0089 3.2911 0.4159 2.7782 0.1933 3.0076 0.0909 2.6549 2.3925 2.5961 1.7939 2.7372 0.9547 2.6330 0.7598 2.6230 1.3108 2.7225 1.3287 2.7944 0.3904 3.3248 0.4192 2.5958 1.5558 2.5958 1.6053 2.6472 1.3935 2.6010 1.8847 3.1181 0.4304 2.7853 0.1987 2.6271 1.5933 2.5408 2.0719 2.6142 1.6386 2.6520 2.0060 2.6075 2.3349 3.0018 0.0908 2.5971 1.5285 2.6421 1.2282 2.6573 2.0333 2.5748 2.5533 2.6086 2.1092 3.0647 0.4426 2.6006 1.8551 2.6126 2.0269 2.7787 0.1969 2.5846 2.0995 3.3489 0.0348 2.7013 0.8115 2.5998 2.0393 2.6187 2.0060 3.0214 0.0914 2.7022 2.0060 2.6024 2.1526 2.6143 2.0089 2.6107 2.0333 2.6114 2.0060 2.6384 2.0333 2.6121 2.0060 2.8541 0.9963 2.5952 2.0269 2.6121 2.0333 2.5701 2.0269 2.5958 2.0333 2.8781 0.9793 2.6034 2.0393 2.6022 2.0269 2.6125 2.0393 2.6088 2.0269 3.3274 0.4303 2.5867 2.0089 2.6001 2.0393 2.5640 2.0089 2.5862 2.0393 2.8316 0.9932 2.6384 0.7826 2.5853 2.0089 2.5277 2.2586 2.5794 2.0089 2.6210 2.0060 2.6420 0.7759 2.5875 2.1294 4.0536 0.0657 2.9179 0.1663 2.5599 2.0333 2.6738 0.1685 2.6238 1.3235 3.8959 0.1300 2.6087 1.6130 2.6200 2.0269 2.6155 1.5834 2.6185 1.3276 2.9276 0.6315 3.1328 0.1017 2.6314 2.0393 2.6343 0.7817 2.9106 0.0950 2.9828 0.5810 2.7504 0.3797 2.5578 2.0089 2.6085 2.0060 2.6023 1.6083 2.5161 2.2033 2.6118 1.6002 2.6115 2.0333 2.5940 1.3431 2.5504 1.7081 2.6065 1.8220 2.6029 2.0269 2.5972 2.1603 2.5680 2.0060 2.6523 0.8701 2.5875 2.0393 2.6015 1.6076 2.6207 2.0333 2.6097 2.1951 2.5859 2.0089 2.6046 2.0060 2.5403 2.0269 2.6217 2.0060 2.5993 2.0333 2.5539 2.0393 2.6081 2.0333 2.5934 2.0269 2.5719 2.0089 2.6243 2.0269 2.5879 2.0393 4.0205 0.1289 2.5925 2.0393 2.5941 2.0089 2.7837 0.9406 2.5760 2.0089 3.2671 0.5626 2.5866 3.1052 4.0869 0.1425 2.5727 1.8994 2.5142 2.2565 2.5871 2.4450 2.9034 0.9881 2.6204 1.7378 2.7731 0.9779 2.5847 2.4917 2.7308 2.0060 2.5680 3.0026 2.6018 2.0333 2.5883 1.7040 2.6157 2.0269 2.5774 2.2325 2.5447 2.0393 2.6121 2.0060 2.5591 2.0089 2.6092 2.0333 1b. Fig. 2, Ti interference Part 2 of 2: 1/7/05, 2/9/05, 2/16/05, 2/23/05 1/7/05 1/7/05 1/7/05 2/9/05 2/9/05 2/9/05 2/16/05 2/16/05 2/16/05 2/23/05 2/23/05 2/23/05 2/23/05 46/43Ca stds[Ca] ODP658[Ca] 46/43Ca stds[Ca] ODP658[Ca] 46/43Ca stds[Ca] ODP658[Ca] 46/43Ca stds[Ca] KNR166-2[Ca] B997-330PC[Ca] 2.6178 2.0060 2.6331 2.0060 2.6107 2.0060 2.6239 2.0060 2.6153 2.0333 2.6086 2.0333 2.5972 2.0333 2.6150 2.0333 2.6078 2.0269 2.5862 2.0269 2.6122 2.0269 2.6007 2.0269 2.5934 2.0393 2.5892 2.0393 2.5862 2.0393 2.5779 2.0393 2.5833 2.0089 2.5732 2.0089 2.5804 2.0089 2.5858 2.0089 2.6338 1.2993 2.5708 2.8330 2.6526 1.2411 2.6343 1.2704 2.6024 1.4992 2.5750 3.2789 2.6702 1.1022 2.6557 0.8642 2.6174 1.4151 2.6026 1.8162 2.6055 1.4520 2.6337 1.3102 2.5982 1.6780 2.5943 2.5839 2.6531 1.0822 2.6663 0.8237 2.5787 2.3914 2.5608 3.4669 2.6438 0.9395 2.6453 1.0837 2.5831 2.2359 2.6098 1.9637 2.6095 1.6169 2.5958 2.1192 2.5883 2.1539 2.6205 1.7135 2.6443 1.7157 2.6087 2.1010 2.6009 2.2093 2.6188 2.1363 2.6364 1.4982 2.6062 2.0060 2.6218 2.0060 2.6155 2.0060 2.6254 2.0060 2.5883 2.0333 2.5886 2.0333 2.6078 2.0333 2.6013 2.0333 2.5990 2.0269 2.6179 2.0269 2.5951 2.0269 2.5978 2.0269 2.5994 2.0393 2.5910 2.0393 2.6140 2.0393 2.5921 2.0393 2.5813 2.0089 2.5947 2.0089 2.5772 2.0089 2.5967 2.0089 2.6291 1.3549 2.5826 2.0396 2.6039 1.8263 2.7533 0.4623 2.6555 0.7429 2.6740 1.0223 2.8615 0.2413 2.0248 2.6575 0.9754 2.6885 1.0431 2.7871 0.2589 2.7950 0.3083 2.6977 0.8235 2.6545 1.0410 2.6218 1.1940 2.6461 1.0759 2.6621 0.8055 2.6384 1.0907 2.6913 0.7941 2.6974 0.6852 2.6683 1.4223 2.9203 0.2360 2.6069 1.5200 2.6305 1.2248 2.5863 2.1128 2.9567 0.2402 2.6277 1.6025 2.6425 1.5858 2.6082 2.1762 2.8584 0.2555 2.5936 2.1052 2.6094 2.0888 2.6146 2.0060 2.5771 2.0060 2.6158 2.0333 2.5813 2.0333 2.5754 2.0269 2.6018 2.0269 2.5938 2.0393 2.5999 2.0393 2.5811 2.0089 2.6084 2.0089 2.7398 1.1324 2.8005 0.7560 2.7237 1.2942 2.7115 0.8046 2.7736 0.9362 2.5804 2.2964 2.5994 2.2147 2.6307 2.0060 2.6341 2.0333 2.5996 2.0269 2.5955 2.0393 2.5819 2.0089 2. Fig. 3, Matrix effects date Standard [Ca]-2.02(mM) Li/Ca dev. Li outliers Mg/Ca dev. Mg outliers Mn/Ca dev. Mn outliers Zn/Ca dev. Zn outliers Sr/Ca dev. Sr outliers Cd/Ca dev. Cd outliers U/Ca dev. U outliers 8/23/04 S1 -1.5897 -0.042538966 0.023283577 0.026870385 0.058401968 -0.000278433 0.030450289 -0.030503149 S2 -1.6008 -0.013788644 0.021247508 0.006905745 0.072517267 0.000579119 0.031537882 -0.015877251 S3 -1.6041 -0.011417004 0.01848617 0.035741819 0.061840411 0.000481031 0.035010674 -0.006840952 S4 -1.5896 0.029807184 0.018520213 0.030935074 0.060110814 0.001551595 0.070883962 0.009293728 S1 -1.0407 -0.025327222 0.019042119 0.030415507 0.016445721 0.002798965 -0.00283471 -0.013142486 S2 -1.0237 -0.000112246 0.015646055 0.03119567 0.025660618 0.002751964 0.028147972 -0.00881894 S3 -1.0653 0.003086834 0.012744507 0.020274255 0.054094979 -7.34138E-05 0.029268446 -0.003761073 S4 -1.0268 -0.005205399 0.011569892 0.01459545 0.00786374 -0.000749605 0.008167214 -0.010404789 8/28/04 S1 -1.0421 -0.002243925 0.018921474 0.03577213 0.058069929 0.010719356 0.05099819 0.027971135 10/2/04 S1 -1.8515 0.002628829 0.047142283 0.091990241 0.120935003 -0.002305305 0.002253703 -0.041497251 S2 -1.8213 -0.017778646 0.023364803 0.041112685 0.03450974 0.006816135 0.00451382 0.006741306 S3 -1.8267 -0.012921772 0.018796175 0.042821486 0.032462088 -0.000177383 0.03339654 0.016419068 S4 -1.8231 -0.007083753 0.017457205 0.036302938 0.035881664 -0.003448356 0.054240436 0.01512182 S1 -1.2441 -0.003051814 0.016929467 0.03782819 0.046995438 0.007200596 0.015021954 0.024005717 S2 -1.2374 0.000674905 0.018255795 0.037067822 0.006492231 -0.001133923 0.007596454 0.001209567 S3 -1.2602 -0.001747206 0.011727214 0.022410471 0.01916354 0.001961833 0.01940097 0.011489377 S4 -1.2383 0.002016582 0.008585945 0.021284244 0.002786588 -0.00149944 0.006952022 0.008416788 S2 -0.4366 0.001777838 0.004956067 0.014088959 0.076038158 -0.000615032 -0.011113581 0.001721753 S3 -0.4642 0.002585905 0.002484013 0.004842569 0.032549209 0.00217458 0.007486735 -0.003982452 S1 0.3149 0.005636705 0.009165623 0.019101719 -0.003132604 -0.013190404 -0.020807317 -0.0673809360 S4 0.5333 0.00944232 -0.001290305 -0.009708475 -0.007241341 -0.008034491 -0.010863598 -0.004274875 12/3/04 S1 -1.9250 -0.018152339 0.026756635 0.043850204 0.14201291 0.011435522 -0.066582559 0.047446825 S2 -1.9292 -0.017240563 0.025440772 0.038245251 0.11755528 -0.00076445 -0.004261836 0.026187735 S3 -1.9291 -0.029179628 0.023582221 0.036506209 0.184816985 0.005191263 0.088010776 0.035915969 S4 -1.9286 -0.00013263 0.021733687 0.035129633 0.064732801 0.000328802 0.059062534 0.0587250002 S1 -0.6924 0.003054236 0.010875175 0.020489829 0.024786923 0.007461392 0.012205967 0.006443256 S2 -0.6965 0.00174572 0.011059155 0.019110707 0.003474505 0.008284226 0.013116107 0.014109201 S3 -0.7092 0.006086706 0.008679499 0.012377363 0.011751308 0.004871634 0.014364977 0.008040192 S4 -0.6769 0.002587889 0.004561934 0.004856661 -0.004729034 -0.004420322 -0.000435397 0.008073728 S1 -0.4267 0.009727968 0.009391245 0.009083165 0.03283465 0.003103076 -0.012903534 -0.017350604 S2 -0.4117 0.000232325 0.007232965 0.006693907 -0.007210679 0.004752358 -0.004987214 0.02368735 S3 -0.4147 0.002075893 0.00341994 0.000726296 0.00301305 -0.002242715 0.004875061 0.001594653 S4 -0.4124 0.000128365 0.003061217 0.009182067 -0.003782349 0.002755277 6.1736E-05 0.008249193 S1 0.0892 0.009917508 0.005055505 -0.002692015 0.019986361 0.004121802 -0.008790385 0.001360316 S2 0.1403 0.002675707 0.00296227 -0.003696971 -0.023308461 0.000668371 -0.013439972 -0.001256316 S3 0.1094 -0.001429662 -0.006348149 -0.00302972 -0.017256071 -0.005007709 -0.005233581 -0.000839539 S4 0.0795 -0.000546735 -0.00056145 -0.00945496 -0.01070745 -0.004309072 -0.001013622 -0.00343789 12/8/04 S1 0.1326 0.001239237 0.005532047 0.002587099 0.008981368 0.007660075 -0.002081444 0.013346481 S2 0.1751 0.00049425 -0.002123873 0.000737719 -0.017188894 0.008620439 -0.006853571 0.008733587 S3 0.2125 -0.006022919 0.000997844 -0.007404512 -0.010971885 0.008969876 -0.007555148 -0.021569359 1/7/05 S1 0.1339 -0.00194705 -0.001308917 0.001382386 0.019046763 0.006384051 -0.003899909 -0.027868171 S2 0.1893 0.002468657 0.005819471 0.001577357 -0.013731664 -0.004200709 -0.031528348 -0.026688569 S3 0.0196 0.008173779 -0.004946281 -0.006231223 -0.021220726 -0.012721772 -0.027451269 -0.013079061 S1 -0.9977 0.007115136 0.019452313 0.041323467 0.063037232 0.026086801 0.007215284 -0.001859499 S2 -0.9769 0.00367121 0.021123345 0.020552711 0.015148664 -0.003727403 -0.004618335 -0.0024385 S3 -0.9790 -0.00472936 0.012641994 0.007277489 -0.008515716 -0.012061475 0.010379553 0.023027511 S4 -0.9293 0.007004776 0.006016224 0.00228296 0.009247547 -0.009235975 -0.005197991 0.027807396 S2 -1.7840 -0.000910162 0.02944099 0.040224048 0.019093905 0.00363155 0.004968069 0.011119231 S3 -1.7798 0.001178152 0.030967017 0.031858292 0.016108363 -0.000792682 0.03237189 0.001749291 S4 -1.7645 0.005594934 0.01861648 0.025727681 0.033317004 -0.010568745 0.034367437 0.003288243 2/9/05 S1 0.1163 -1.25613E-05 0.006636272 0.003140354 0.019584328 0.002109986 -0.001110598 -0.005563786 S2 0.0852 0.003051655 -0.002890288 0.005871172 0.003128072 0.006682183 -0.002971064 0.013936054 2/16/05 S1 -0.5218 -0.010154993 0.013090111 0.018302259 0.030756302 0.001768589 0.002414071 -0.010362553 S2 0.0688 0.005245346 0.001973494 -0.000631277 -0.019767882 0.013838744 -0.00076375 0.038478918 3. bulloides MgCa vs. size CaCO3 mass(ug) Mg/Ca(mmol/mol) 1.4 3.27 1.7 17.50 3.3 3.70 5.1 2.48 6.4 2.49 6.5 3.13 7.1 2.31 8.3 2.32 12.2 3.09 19.0 2.77 19.5 2.44 19.6 3.10 22.1 3.43 28.1 2.93 29.0 2.89 29.2 2.63 31.6 2.86 35.3 2.67 38.8 2.98 40.1 3.28 40.6 2.97 40.9 2.87 43.6 3.09 47.0 2.46 48.7 2.54 49.1 3.14 49.9 2.78 51.2 2.85 57.4 2.87 58.5 2.74 59.4 2.73 60.2 2.94 61.4 2.48 62.9 2.80 66.4 3.09 67.6 2.87 68.1 3.04 69.7 2.91 69.7 3.01 71.9 3.06 72.5 2.52 72.9 2.71 73.6 2.91 74.4 2.31 74.7 2.90 75.3 2.54 75.3 3.32 75.4 3.03 76.2 2.49 76.4 2.30 77.3 3.12 77.3 2.90 78.9 2.52 79.6 2.06 80.0 3.15 80.6 3.07 81.9 3.09 82.1 2.72 82.4 3.00 85.4 2.37 86.1 2.96 86.6 2.58 86.6 2.81 89.3 3.36 89.7 2.89 89.8 2.79 90.2 2.51 90.8 2.91 91.1 3.09 92.0 2.69 92.8 2.62 92.8 2.74 94.2 2.68 94.7 2.99 94.9 3.13 95.7 3.01 96.2 2.72 98.1 3.14 99.3 2.82 102.6 2.99 103.6 2.55 105.2 2.50 110.2 2.93 111.8 3.05 111.8 3.47 112.8 2.47 112.9 2.74 113.1 2.86 113.7 2.89 118.3 4.43 119.6 2.50 122.8 2.73 122.9 2.96 130.0 2.86 130.2 2.67 136.9 3.16 138.5 2.94 140.4 2.99 145.7 3.07 157.0 2.91