It has been shown that some of the fluorinated ethane derivatives being introduced as CFC-replacements can be transformed to TFA (trifluoroacetate) in the atmosphere. Moreover, TFA is extremely stable in the environment, and this has raised questions regarding how widespread TFA is in the environment. We found that TFA is ubiquitous in precipitation: samples of rain from Ireland and Poland and snow from Canada, Sweden, New Zealand, and East Antarctica contained 1-1100 ng/L, and, studying a firn core drilled in Antarctica, concentrations of 3-56 ng/L were measured in layers formed during the 19th century. We have confirmed the preindustrial presence of significant background concentrations of trifluoroacetate in historic precipitation samples from the analysis of firn. Extensive procedures were enforced to prevent sample contamination.

A firn core was drilled in Dronning Maud Land, Antarctica, to investigate the presence of haloacetates in snow that had accumulated over the past 200 years. By employing GC-MS detection of methyl esters of haloacetic acids, we were able to measure haloacetate concentrations down to one or a few nanograms per liter. Trichloroacetate (TCA) and dibromoacetate (DBA) were found in firn at concentrations that clearly exceeded the blank level of the applied analytical procedure, with mean concentrations estimated to 12 and 6 ng/L, respectively. There were also indications that mono-and dichloroacetate (MCA and DCA) were present in firn, whereas monobromoacetate (MBA) was found only in samples of surficial snow. We concluded that there is a significant natural background level of TCA and DBA in precipitation based on the following: (i) several of samples represented snow accumulated in the 19th century; (ii) haloacetates can be expected to be immobile in Antarctic firn; (iii) extensive measures were taken to prevent sample contamination; and (iv) blank levels of the analytical procedure used were low and stable. In addition, our results suggested that MCA and DCA also occur naturally in precipitation.