Hydroclimatic record from an Altiplano cushion peatland (24°S) indicates large-scale reorganisation of atmospheric circulation for the late Holocene.

The hydroclimate of South America is characterized by the South American summer monsoon (SASM), a tropical atmospheric circulation that induces a summer precipitation regime, and the Southern Hemisphere Westerlies (SHW), an extratropical atmospheric circulation that induces a winter precipitation regime. Stretched between these two systems is a NW-SE-oriented region dominated by descending air masses, resulting in the South American subtropical dry zone (SASDZ), also known as the arid diagonal. We investigated the Cerro Tuzgle cushion peatland (CTP) located on the Argentine Altiplano, north of the present-day SASDZ. Previous work revealed that the CTP was consistently in the SASM regime during the last 2900 cal yr BP. Here, we extend the CTP record to the middle Holocene covering the last 7200 cal yr BP to gain further knowledge of the Holocene development of the SASM and potential modulations of the SASDZ. The prominent feature of the entire record is a distinct and lasting transition centred around 3100 cal yr BP characterized by declining minerogenic content, increasing organic carbon content, rising stable carbon isotope values of organic matter and cellulose, and increasing stable oxygen isotope values of cellulose. We interpret this specific proxy pattern as a hydroclimatic transition towards less arid conditions at the CTP after 3100 cal yr BP. The transition corresponds with the end of the continuous Holocene strengthening of the SASM between 3500 cal yr BP and 3000 cal yr BP indicated by proxy records from north and east of the CTP. The CTP does not reflect this strengthening of the SASM and rather exhibits a threshold response indicating the effective establishment of the SASM summer precipitation regime at 24°S. This suggests that moisture supply during a more arid middle Holocene was provided by isotopically depleted precipitation, while moisture supply after the transition originated from isotopically enriched SASM summer precipitation. Concurrent hydroclimatic changes in the SHW winter precipitation regime south of the SASDZ are documented in a distinct lake level rise of Laguna Aculeo (33°50´S) around 3200 cal yr BP. These coinciding hydrological changes of the SASM and the SHW precipitation regimes indicate larger scale reorganisations of atmospheric circulation components, potentially connected to major modulations of the SASDZ. Thus, our CTP record sheds light on the middle to late Holocene development of the SASM at its southern limit and corroborates connections between the tropical and extratropical hydroclimate of South America.

3,3'-Dihydroxyisorenieratene prevents UV-induced formation of reactive oxygen species and the release of protein-bound zinc ions in human skin fibroblasts.

3,3'-Dihydroxyisorenieratene (DHIR) is a structurally unusual carotenoid exhibiting bifunctional antioxidant properties. It is synthesized by Brevibacterium linens, used in dairy industry for the production of red smear cheeses. The compound protects cellular structures against photo-oxidative damage and inhibits the UV-dependent formation of thymidine dimers. Here we show that DHIR prevents a UV-induced intracellular release of zinc ions from proteins in human dermal fibroblasts. The effect is correlated with a decreased formation of intracellular reactive oxygen species. In contrast, zinc release from cellular proteins induced by hyperthermia is not affected by pretreatment of cells with the antioxidant DHIR. It is suggested that the intracellular zinc release upon UV irradiation is due to oxidative modifications of the zinc ligands in proteins (e.g. cysteine) and that protection by DHIR is due to intracellular scavenging of reactive oxygen species generated in photo-oxidation.

Spectroscopic properties of phenolic and quinoid carotenoids: a combined theoretical and experimental study.

For the natural carotenoid 3,3'-dihydroxyisorenieratene (DHIR) and two synthetic derivatives, 3,3'-dihydroxy-16,17,18,16',17',18'-hexanor-Phi,Phi-carotene (DHHC) and Phi,Phi-carotene-3,3'-dione (DHIRQ, isorenieratene-3,3'-dione), steady state absorption experiments and combined density functional and multi-reference configuration interaction calculations were carried out. In addition, femtosecond transient absorption spectra were recorded for DHIR. Due to their marked out-of-plane distortion in DHIR, the phenolic end groups participate only partially in the conjugation system. In the low-energy regime its absorption spectrum with the maximum at 21 700 cm(-1) in acetone solution therefore closely resembles that of beta-carotene, the same as for the T1 energy. Further similarities are also found for the decay kinetics of the optically bright 1(1)Bu+ state of these compounds. After femtosecond excitation, the 1(1)Bu+ population of DHIR decays with a lifetime of 110 fs to the vibrationally hot 2(1)Ag-,v state which in turn relaxes to the 2(1)Ag-,0 state within 500 fs. Decay of the 2(1)Ag-,0 state to the S0 state occurs at a time scale of 12 ps. Demethylation of the phenolic end groups alleviates the steric repulsion by the polyene chain and causes a small red shift (1000 cm(-1)) comparing the absorption spectra of DHHC and DHIR. Oxidation of DHIR leads to drastic changes of the electronic and geometric properties. The quinoid end groups of DHIRQ are fully integrated into the conjugation system, shifting the absorption maximum to 17 800 cm(-1) in acetone solution which thus takes a blue color. The results of the quantum chemical calculations indicate that, in addition to the 2(1)Ag-(S1) state, two dark internal charge-transfer singlet states and the 1(1)Bu- state might be located energetically below the optically bright 1(1)Bu+ (S5) state of DHIRQ.