An ink dating method based on solvent analysis was recently developed using thermal desorption followed by gas chromatography/mass spectrometry (GC/MS) and is currently implemented in several forensic laboratories. The main aims of this work were to implement this method in a new laboratory to evaluate whether results were comparable at three levels: (i) validation criteria, (ii) aging curves, and (iii) results interpretation. While the results were indeed comparable in terms of validation, the method proved to be very sensitive to maintenances. Moreover, the aging curves were influenced by ink composition, as well as storage conditions (particularly when the samples were not stored in "normal" room conditions). Finally, as current interpretation models showed limitations, an alternative model based on slope calculation was proposed. However, in the future, a probabilistic approach may represent a better solution to deal with ink sample inhomogeneity.

For more than a decade scientists tried to develop methods capable of dating ink by monitoring the loss of phenoxyethanol (PE) over time. While many methods were proposed in the literature, few were really used to solve practical cases and they still raise much concern within the scientific community. In fact, due to the complexity of ink drying processes it is particularly difficult to find a reliable ageing parameter to reproducibly follow ink ageing. Moreover, systematic experiments are required in order to evaluate how different factors actually influence the results over time. Therefore, this work aimed at evaluating the capacity of four different ageing parameters to reliably follow ink ageing over time: (1) the quantity of solvent PE in an ink line, (2) the relative peak area (RPA) normalising the PE results using stable volatile compounds present in the ink formulation, (3) the solvent loss ratio (R%) calculated from PE results obtained by the analyses of naturally and artificially aged samples, (4) a modified solvent loss ratio version (R%*) calculated from RPA results. After the determination of the limits of reliable measurements of the analytical method, the repeatability of the different ageing parameters was evaluated over time, as well as the influence of ink composition, writing pressure and storage conditions on the results. Surprisingly, our results showed that R% was not the most reliable parameter, as it showed the highest standard deviation. Discussion of the results in an ink dating perspective suggests that other proposed parameters, such as RPA values, may be more adequate to follow ink ageing over time.

The development of ink dating methods requires an important amount of work in order to be reliably applicable in practice. Major tasks include the definition of ageing parameters to monitor ink ageing. An adequate parameter should ideally fulfil the following criteria: it should evolve as a function of time in a monotonic way, be measurable in a majority of ink entries, be as accurate and reproducible as possible, and finally it should not be influenced too much by transfer and storage conditions. This work aimed at evaluating the potential of seven ageing parameters for ink dating purposes: the phenoxyethanol quantity, relative peak areas (RPA), three solvent loss ratios (R%, R%*, NR%) and two solvent loss parameters (R NR). These were calculated over approximately one year for 25 inks selected from a large database to represent different ageing behaviours. Ink entries were analysed using liquid extraction followed by GC/MS analysis. Results showed that natural ageing parameters (NR% and NR) were not suitable ageing parameters for ink entries older than a few weeks. RPA used other compounds present in ink formulations in combination to PE in order to normalise the results. However, it presented particular difficulties as they could not be defined for all inks and were thus applicable only for 64% of the studied inks. Finally, the PE quantity, R% and R allowed to follow the ageing of the selected inks over the whole time frame and were identified as the most promising. These were thus selected to test three different interpretation models in the second part of this article. The possibilities and limitations of ink dating methods will be discussed in a legal perspective.

The development of an ink dating method requires an important investment of resources in order to step from the monitoring of ink ageing on paper to the determination of the actual age of a questioned ink entry. This article aimed at developing and evaluating the potential of three interpretation models to date ink entries in a legal perspective: (1) the threshold model comparing analytical results to tabulated values in order to determine the maximal possible age of an ink entry, (2) the trend tests that focusing on the "ageing status" of an ink entry, and (3) the likelihood ratio calculation comparing the probabilities to observe the results under at least two alternative hypotheses. This is the first report showing ink dating interpretation results on a ballpoint be ink reference population. In the first part of this paper three ageing parameters were selected as promising from the population of 25 ink entries aged during 4 to 304days: the quantity of phenoxyethanol (PE), the difference between the PE quantities contained in a naturally aged sample and an artificially aged sample (R) and the solvent loss ratio (R%). In the current part, each model was tested using the three selected ageing parameters. Results showed that threshold definition remains a simple model easily applicable in practice, but that the risk of false positive cannot be completely avoided without reducing significantly the feasibility of the ink dating approaches. The trend tests from the literature showed unreliable results and an alternative had to be developed yielding encouraging results. The likelihood ratio calculation introduced a degree of certainty to the ink dating conclusion in comparison to the threshold approach. The proposed model remains quite simple to apply in practice, but should be further developed in order to yield reliable results in practice.