Measurements of CFC-11, CFC-12, and HCFC-22 total columns in the atmosphere at the St. Petersburg site in 2009–2019

Abstract

Abstract. The retrieval strategies for deriving the atmospheric total columns (TCs) of CFC-11 (CCl3F), CFC-12 (CCl2F2), and HCFC-22 (CHClF2) from ground–based measurements of IR solar radiation have been improved. We demonstrate the advantage of using the Tikhonov-Phillips regularization approach for solving the inverse problem of the retrieval of these gases and give the optimized values of regularization parameters. The estimates of relative systematic and random errors amount to 7.61 % and 3.08 %, 2.24 % and 2.40 %, 5.75 % and 3.70 %, for CFC-11, CFC-12, and HCFC-22, respectively. We analyze the time series of the TCs and mean molar fractions (MMFs) of CFC-11, CFC-12, and HCFC-22 measured at the NDACC site St. Petersburg located near Saint Petersburg, Russia for the period of 2009–2019. Mean values of the MMFs for CFC-11, CFC-12, and HCFC-22 total 225, 493, and 238 pptv, respectively. Estimates of the MMFs trends for CFC-11, CFC-12, and HCFC-22 account for −0.40 ± 0.07 %/yr, -0.49 ±0.05 %/yr, and 2.12±0.13 %/yr, respectively. We have compared the mean values, trends and seasonal variability of CFC-11, CFC-12, and HCFC-22 MMFs measured at the St. Petersburg site in 2009–2019 to that of 1) near–ground volume mixing ratios (VMRs) measured at the observational site Mace Head, Ireland (GVMR); 2) the mean in the 8–12 km layer VMRs measured by ACE–FTS and averaged over 55–65° N latitudes (SVMR); and the MMFs of the Whole Atmosphere Community Climate Model for the St. Petersburg site (WMMF). The means of the MMFs are less than that of the GVMR for CFC-11 by 9 pptv (3.8 %), for CFC-12 by 24 pptv (4.6 %); for HCFC-22, the mean MMFs does not differ significantly from the mean GVMR. The absolute value of the trend estimates of the MMFs is less than that of the GVMR for CFC-11 (−0.40 vs −0.53 %/yr) and CFC-12 (−0.49 vs −0.59 %yr); the trend estimate of the HCFC-22 MMFs does not differ significantly from that of the GVMR. The seasonal variability of the GVMR for all three gases is much lower than the MMFs variability. The means of the MMFs are less than that of the SVMR for CFC-11 by 10 pptv (4.3 %), for CFC-12 by 33 pptv (6.3 %), and for HCFC-22 by 2 pptv (0.8 %). The absolute value of the trend estimates of the MMFs is less than that of the SVMR for CFC-11 (−0.40 vs −0.63 %/yr) and CFC-12 (−0.49 vs −0.58 %/yr); the trend estimate of the HCFC-22 MMFs does not differ significantly from that of the SVMR. The MMF and SVMR values show nearly the same qualitative and quantitative seasonal variability for all three gases. The means of the MMFs are greater than that of the WMMF for CFC-11 by 22 pptv (10 %), for CFC-12 by 15 pptv (3.1 %), and for HCFC-22 by 23 pptv (10 %). The absolute value of the trend estimates of the MMFs is less than that of the WMMF for CFC-11 (−0.40 vs −1.68 %/yr), CFC-12 (−0.49 vs −0.84 %/yr), and HCFC-22 (2.12 %/yr vs 3.40 %/yr). The MMFs and WMMF values show nearly the same qualitative and quantitative seasonal variability for CFC-11 and CFC-12, whereas the seasonal variability of the WMMF for HCFC-22 is essentially less than that of the MMFs. In general, the comparison of the MMFs with the independent data shows a good agreement of their means within the systematic error of considered measurements. The observed trends over the St. Petersburg site demonstrate the smaller decrease rates for CFC-11 and CFC-12 TCs than that of the independent data, and the same decrease rate for HCFC-22. The suggested retrieval strategies can be used for analysis of the IR solar spectra measurements using Bruker FS125HR spectrometers, e.g. at other IRWG sites of the NDACC observational network.