Update: I finally got motivated and fixed the TOC analyzer (long story short, there was no motivation on my behalf to get it fixed (since we REALLY don't use it much at work anymore) and a complicated set of problems to be fixed...). Here are the results from the samples analyzed.
But before that, a few caveats... (1) the metals analysis is still valid. The metals have a holding time of 6 months (except Hg) when preserved with HNO3 so those are still good. (2) the TOC samples were preserved with HCl when i got them, so technically, they should be still good. That said, they are over the recommended holding time of 30 days, so there's no way to really know. In order to see how well the preserved samples hold up over time, i am going to analyze them all again in a few months time and then we can compare the results.
Looking at the aquarium results and comparing them with the TOC analysis results at work, the one thing that can give us some insight of the quality of the results was the matrix spike & matrix spike duplicate QA/QC results. A matrix spike/matrix spike duplicate (MS/MSD) is when you add a known quantity of the analyte (10 ppm TOC in this case) to a sample and then calculate the % recovery of the matrix spikes versus the original sample and to each other (acceptable results are
+25% of the theoretical value).
For the samples that were prepared and analyzed right away (i.e. prior to the TOC machine breaking), the MS/MSD % recoveries are typically been between 90-105% recovery. For the samples that were prepared and analyzed much later (i.e. after the TOC machine broke), the MS/MSD % recoveries were more erratic - from 37%-127% recovery (64%-114% if we exclude the highest and lowest % recoveries). Of the 10 MS/MSD solutions prepared, only 3 were outside the acceptable % recovery range of 75-125% and the average % recovery was actually 90%.
The take away message of this all? The results should be interpreted with a grain of salt but are probably fairly accurate (though of course we have no way to find out).
Code:
| New Samples | Al | B | Cu | Fe | Mn | Mo | Zn |
| CA Tank 10/18/13 | 0.02| 0.12| < | 0.30| < | < | 0.09|
| CA Tank 10/23/13 | < | 0.13| < | 0.03| < | < | 0.09|
| CA Tank 10/23/13 | < | 0.12| < | 0.14| < | < | 0.08|
| CA Tank 10/30/13 | < | 0.13| < | 0.20| < | < | 0.27|
| CA Tank 10/30/13 | < | 0.10| < | 0.02| < | < | 0.03|
| CA Tank 11/13/13 | < | 0.13| < | 0.05| < | < | 0.03|
| CA Tank 11/22/13 | < | 0.12| < | 0.13| < | < | 0.03|
| CA Tank 12/12/13 | < | 0.12| < | 0.01| < | < | 0.05|
| UDGags Tap 1/13/14 | < | < | 0.04| < | < | < | 0.01|
| UDGags Tank 1/13/14 | 0.05| 1.5| 0.18| 11 | 0.03| 0.09| 0.57|
| New Samples | TOC | K | Ca | Mg |Gen. Hard.| Comments |
| CA Tank 10/18/13 | 11.0| 28 | 16 | 4.5| 8.6 dGH | |
| CA Tank 10/23/13 | 13.1| 36 | 24 | 5.8| 4.7 dGH | Before WC |
| CA Tank 10/23/13 | 12.1| 28 | 16 | 4.6| 3.2 dGH | After WC |
| CA Tank 10/30/13 | 13.0| 34 | 22 | 5.3| 4.3 dGH | Before WC |
| CA Tank 10/30/13 | 9.9| 26 | 15 | 4.1| 3.1 dGH | After WC |
| CA Tank 11/13/13 | 10.4| 31 | 18 | 4.6| 3.6 dGH | Before WC |
| CA Tank 11/22/13 | 8.0| 32 | 18 | 4.2| 3.5 dGH | Before WC |
| CA Tank 12/12/13 | 8.9| 33 | 20 | 4.2| 3.8 dGH | Before WC |
| UDGags Tap 1/13/14 | 1.2| 2.8| 18 | 29 | 8.8 dGH | |
| UDGags Tank 1/13/14 | 22.4| 78 | 20 | 26 | 9.2 dGH | Before WC |
p.s. i haven't been following this conversation in quite a while since i've just been focused on other things (@ work and @ home - it's gardening season!). i have some thoughts and comments on things, but will post those things later since i just wanted to get this information out first.
p.p.s. another thing that i noticed. when i prepared the samples for analysis, i forgot to preserve a sample for duplicate analysis (as part of our standard QA/QC protocol). So i just poured a duplicate of UDGags Tank 1/13/14 into a vial (which was UNPRESERVED) and analyzed that as the duplicate. The sample value (preserved) was 22.4 ppm TOC. The duplicate value (unpreserved) was 2.2 ppm TOC. This just shows that the acid preservative was doing something... we just don't know how well it worked...