UV radiation biomonitoring using cell compartmentation of UV-absorbing compounds in herbarium samples of a liverwort

Resumen

Ultraviolet-absorbing compounds (UVACs) were analyzed in 90 herbarium samples of the liverwort Jungermannia exsertifolia subsp. cordifolia collected throughout Spain in the period 1913-2006, in order to evaluate their usefulness in UV radiation biomonitoring. This was assessed, for the first time in bryophytes, differentiating the soluble (mainly vacuolar) and insoluble (cell wall-bound) UVACs (respectively, SUVACs and IUVACs), which may represent different mechanisms to cope with UV radiation. The bulk levels of SUVACs and IUVACs, and the concentrations of seven individual compounds (five SUVACs and two IUVACs) were analyzed, and several environmental variables of the sampling points were obtained: longitude, latitude, altitude, ozone column, and modelled UV levels. Diverse positive relationships of UVAC variables with UV radiation levels were identified in both the temporal and spatial scales. The soluble compound p-coumaroylmalic acid showed significantly higher concentrations in the years after the onset of stratospheric ozone degradation (around 1975) with respect to the previous years. The bulk level and the concentrations of three individual SUVACs were higher in the Spanish samples analyzed in the present study than in the northern European samples analyzed in a previous study in which IUVACs were not considered. The bulk level of IUVACs was the biological variable best spatially correlated with the UV exposure of the samples and with important factors determining it, such as altitude and latitude. Furthermore, the bulk level of IUVACs was the biological variable selected by a stepwise multiple linear regression analysis to reconstruct the past levels of UV-B radiation. The reconstructed UV-B did not show a clear trend in the period 1913-2006, which was coincident with other climatic and biological UV reconstructions. Both SUVACs and IUVACs were significant loading factors differentiating summer and autumn samples in the Principal Components Analysis conducted using both UVACs and the environmental variables, but again the bulk level of IUVACs was the main loading factor differentiating the samples collected from the highest and most UV-exposed localities (Sierra Nevada). In general, these findings suggest that UVACs were stimulated by increased UV levels in time or space, and that IUVACs would be better UV protectants than SUVACs, probably due to their more efficient screening capacity. Overall, UVACs of J. exsertifolia subsp. cordifolia were good UV biomarkers, and their location in the soluble or cell wall-bound fractions determined their usefulness in the different aspects of UV biomonitoring, including the assessment of the UV-B increase associated to anthropogenic ozone degradation.