Pronounced occurrence of long-chain alkenones and dinosterol in a 25,000-year lipid molecular fossil record from Lake Titicaca, South America

Our analysis of lipid molecular fossils from a Lake Titicaca (16° S, 69° W) sediment core reveals distinct changes in the ecology of the lake over an ∼25,000-yr period spanning latest Pleistocene to late Holocene time. Previous investigations have shown that over this time period Lake Titicaca was subject to large changes in lake level in response to regional climatic variability. Our results indicate that lake algal populations were greatly affected by the changing physical and chemical conditions in Lake Titicaca. Hydrocarbons are characterized by a combination of odd-numbered, mid- to long-chain (C₂₁-C₃₁) normal alkanes and alkenes. During periods when lake level was higher (latest Pleistocene, early Holocene, and late Holocene), the C₂₁n-alkane, and the C₂₅ and C₂₇ alkenes dominate hydrocarbon distributions and indicate contribution from an algal source, potentially the freshwater alga Botryococcus braunii. The C₃₀ 4 α-methyl sterol (dinosterol) increases sharply during the mid-Holocene, suggesting a greatly increased dinoflagellate presence at that time. Long-chain alkenones (LCAs) become significant during the early Holocene and are highly abundant in mid-Holocene samples. There are relatively few published records of LCA detection in lake sediments but their occurrence is geographically widespread (Antarctica, Asia, Europe, North America). Lake Titicaca represents the first South American lake and the first low-latitude lake in which LCAs have been reported. LCA abundance and distribution may be related to the temperature-dependent response of an unidentified algal precursor. Although the LCA unsaturation indices cannot be used to determine absolute Lake Titicaca temperatures, we suspect that the published LCA U₃₇^K unsaturation calibrations can be applied to infer relative temperatures for early to mid-Holocene time when LCA concentrations are high. Using these criteria, the U₃₇^K unsaturation indices suggest relatively warmer temperatures in the mid-Holocene. In contrast to previous speculation, lipid analysis provides little evidence of a greatly increased presence of aquatic plants during the mid-Holocene. Instead, it appears that a few algal species were dominant in the lake. Based on the dramatic rise in abundances of LCAs and dinosterol during the early to mid-Holocene, we suspect that the algal producers of these compounds rose in response to a combination of physical and chemical changes in the lake. These include temperature, salinity, and alkalinity changes that occurred as lake level dropped sharply during a multi-millennial drought affecting the Central Andean Altiplano.     

A high-resolution TEM-AEM, pH titration, and modeling study of Zn coprecipitation with ferrihydrite

Experiments of Zn²⁺ and Fe³⁺ coprecipitation as a function of pH were conducted in the laboratory at ambient temperature and pressure. X-ray diffraction patterns of the coprecipitates show two broad peaks at 0.149 and 0.258 nm, which is consistent with published patterns for pure 2-line ferrihydrite. Zn²⁺ uptake occurred at pH ≥5 while Fe³⁺ precipitation occurred between pH 3 and 4, although both Zn²⁺ and Fe³⁺ were present in the same solution during the entire range of pH titration. High-resolution transmission electron microscopy shows that the coprecipitates are 2 to 6 nm sized single crystalline particles but aggregated to 50 to 400 nm sized clusters. Analytical electron microscopy indicated that the 5% atomic Zn with respect to Fe was homogeneously distributed. No segregated phases were found in the clusters or at single crystal edges, which is consistent with published extended X-ray absorption fine structure (EXAFS) results at similar Zn/(Zn + Fe) ratios. Hence, occlusion and surface precipitation may be excluded as possible coprecipitation mechanisms. The bulk solution Zn²⁺ sorption edge was fitted to both solid solution and generalized diffuse layer surface complexation models. However, a solid solution model is inconsistent with published EXAFS results that show tetrahedral polydentate Zn²⁺ complexes sharing apices with Fe³⁺octahedra.     

The carbon and sulfur cycles and atmospheric oxygen from middle Permian to middle Triassic

The results of a theoretical isotope mass balance model are presented for the time dependence of burial and weathering-plus-degassing fluxes within the combined long-term carbon and sulfur cycles. Averaged data for oceanic δ¹³C and δ³⁴S were entered for every million years from 270 to 240 Ma (middle Permian to middle Triassic) to study general trends across the Permian-Triassic boundary. Results show a drop in the rate of global organic matter burial during the late Permian and a predominance of low values during the early-to-middle Triassic. This overall decrease with time is ascribed mainly to epochs of conversion of high biomass forests to low biomass herbaceous vegetation resulting in a decrease in the production of terrestrially derived organic debris. Additional contributions to lessened terrestrial carbon burial were increased aridity and a drop in sea level during the late Permian which led to smaller areas of low-lying coastal wetlands suitable for coal and peat deposition.Mirroring the drop in organic matter deposition was an increase in the burial of sedimentary pyrite, and a dramatic increase in the calculated global mean ratio of pyrite-S to organic-C. High S/C values resulted from an increase of deposition in marine euxinic basins combined with a decrease in the burial of low-pyrite associated terrestrial organic matter. The prediction of increased oceanic anoxia during the late Permian and early Triassic agrees with independent studies of the composition of sedimentary rocks.Weathering plus burial fluxes for organic carbon and pyrite sulfur were used to calculate changes in atmospheric oxygen. The striking result is a continuous drop in O₂ concentration from ∼30% to ∼13% over a twenty million year period. This drop was brought about mainly by a decrease in the burial of terrestrially derived organic matter. but with a possible contribution from the weathering of older organic matter on land. It must have exerted a considerable influence on animal evolution because of the role of O₂ in respiration. Some examples are the extinction of many vertebrates, loss of giant insects and amphibians, and the restriction of animals to low elevations. It is concluded that the extinction of plants may have contributed to the extinction of animals.     

Devon's desert ‘worms’

Worm‐like trace fossils, sometimes of large size, have regularly been reported from the otherwise generally poorly‐fossiliferous Permo‐Triassic continental red beds of the East Devon coast, southwest England. Selected examples are discussed here to outline the difficulties involved in elucidating the true producers of these burrows and interpreting their significance in the local palaeoenvironment.     

Differential response at the seafloor during Palaeocene and Eocene ocean warming events at Walvis Ridge,Atlantic Ocean (ODP Site 1262)

The Latest Danian Event (LDE, c. 62.1 Ma) is an early Palaeogene hyperthermal or transient (<200 ka) ocean warming event. We present the first deep‐sea benthic foraminiferal faunal record to study deep‐sea biotic changes together with new benthic (Nuttallides truempyi) stable isotope data from Walvis Ridge Site 1262 (Atlantic Ocean) to evaluate whether the LDE was controlled by similar processes as the minor early Eocene hyperthermals. The spacing of the double negative δ¹³C and δ¹⁸O excursion and the slope of the δ¹⁸O–δ¹³C regression are comparable, strongly suggesting a similar orbital control and pacing of eccentricity maxima as well as a rather homogeneous carbon pool. However, in contrast to early Eocene hyperthermals, the LDE exhibits a remarkable stability of the benthic foraminiferal fauna. This lack of benthic response could be related to the absence of threshold‐related circulation changes or better pre‐adaptation to elevated deep‐sea temperatures, as the LDE was superimposed on a cooling trend, in contrast to early Eocene warming.     

Including spatial distribution in a data‐driven rainfall‐runoff model to improve reservoir inflow forecasting in Taiwan

Multi‐step ahead inflow forecasting has a critical role to play in reservoir operation and management in Taiwan during typhoons as statutory legislation requires a minimum of 3‐h warning to be issued before any reservoir releases are made. However, the complex spatial and temporal heterogeneity of typhoon rainfall, coupled with a remote and mountainous physiographic context, makes the development of real‐time rainfall‐runoff models that can accurately predict reservoir inflow several hours ahead of time challenging. Consequently, there is an urgent, operational requirement for models that can enhance reservoir inflow prediction at forecast horizons of more than 3 h. In this paper, we develop a novel semi‐distributed, data‐driven, rainfall‐runoff model for the Shihmen catchment, north Taiwan. A suite of Adaptive Network‐based Fuzzy Inference System solutions is created using various combinations of autoregressive, spatially lumped radar and point‐based rain gauge predictors. Different levels of spatially aggregated radar‐derived rainfall data are used to generate 4, 8 and 12 sub‐catchment input drivers. In general, the semi‐distributed radar rainfall models outperform their less complex counterparts in predictions of reservoir inflow at lead times greater than 3 h. Performance is found to be optimal when spatial aggregation is restricted to four sub‐catchments, with up to 30% improvements in the performance over lumped and point‐based models being evident at 5‐h lead times. The potential benefits of applying semi‐distributed, data‐driven models in reservoir inflow modelling specifically, and hydrological modelling more generally, are thus demonstrated. Copyright © 2012 John Wiley & Sons, Ltd.     

Likely effects of climate change on groundwater availability in a Mediterranean region of Southeastern Spain

Groundwater resources are typically the main fresh water source in arid and semi‐arid regions. Natural recharge of aquifers is mainly based on precipitation; however, only heavy precipitation events (HPEs) are expected to produce appreciable aquifer recharge in these environments. In this work, we used daily precipitation and monthly water level time series from different locations over a Mediterranean region of Southeastern Spain to identify the critical threshold value to define HPEs that lead to appreciable aquifer recharge in this region. Wavelet and trend analyses were used to study the changes in the temporal distribution of the chosen HPEs (≥20 mm day^?1) over the observed period 1953–2012 and its projected evolution by using 18 downscaled climate projections over the projected period 2040–2099. The used precipitation time series were grouped in 10 clusters according to similarities between them assessed by using Pearson correlations. Results showed that the critical HPE threshold for the study area is 20 mm day^?1. Wavelet analysis showed that observed significant seasonal and annual peaks in global wavelet spectrum in the first sub‐period (1953–1982) are no longer significant in the second sub‐period (1983–2012) in the major part of the ten clusters. This change is because of the reduction of the mean HPEs number, which showed a negative trend over the observed period in nine clusters and was significant in five of them. However, the mean size of HPEs showed a positive trend in six clusters. A similar tendency of change is expected over the projected period. The expected reduction of the mean HPEs number is two times higher under the high climate scenario (RCP8.5) than under the moderate scenario (RCP4.5). The mean size of these events is expected to increase under the two scenarios. The groundwater availability will be affected by the reduction of HPE number which will increase the length of no aquifer recharge periods (NARP) accentuating the groundwater drought in the region. Copyright © 2016 John Wiley & Sons, Ltd.     

The use of geological materials in ancient and contemporary art

Mineral‐based pigments have been used for cave paintings and rock art dating as far back as 70–100 ka in Blombos Cave, South Africa. Ancestral indigenous artists used ochre (clay + Fe oxides and hydroxides) for red and yellow pigments in cave art on every inhabited continent for at least 15 000 years, and much longer than that in some localities. Early historic cultures throughout the Middle East, Asia and the Mediterranean basin added other colourful minerals to their palette, including azurite and malachite for blue and green, calcite, gypsum, and diatomaceous earth for white, and charcoal for black. Some of these cultures created additional pigments by roasting or smelting minerals and altering them with vinegar or other organic acids. The use of mineral pigments and pigments of altered minerals using heat and acid continued throughout the Middle Ages and the Renaissance. Similar mineral pigments were used by native peoples in the New World for rock and cave art. Ancestral artists traditionally used water, saliva, oil and fats as binders for their pigments to create their paint.     

The role of baseflow in dissolved solids delivery to streams in the Upper Colorado River Basin

Salinity has a major effect on water users in the Colorado River Basin, estimated to cause almost $300 million per year in economic damages. The Colorado River Basin Salinity Control Program implements and manages projects to reduce salinity loads, investing millions of dollars per year in irrigation upgrades, canal projects, and other mitigation strategies. To inform and improve mitigation efforts, there is a need to better understand sources of salinity to streams and how salinity has changed over time. This study explores salinity in the baseflow fraction of streamflow, assessing whether groundwater is a significant contributor of dissolved solids to streams in the Upper Colorado River Basin (UCRB). Chemical hydrograph separation was used to estimate baseflow discharge and baseflow dissolved solids loads at stream gages (n = 69) across the UCRB. On average, it is estimated that 89% of dissolved solids loads originate from the baseflow fraction of streamflow, indicating that subsurface transport processes play a dominant role in delivering dissolved solids to streams in the UCRB. A statistical trend analysis using weighted regressions on time, discharge, and season was used to evaluate changes in baseflow dissolved solids loads in streams (n = 27) from 1986 to 2011. Decreasing trends in baseflow dissolved solids loads were observed at 63% of streams. At the three most downstream sites, Green River at Green River, UT, Colorado River at Cisco, UT, and the San Juan River near Bluff, UT, baseflow dissolved solids loads decreased by a combined 823,000 metric tons (mT), which is approximately 69% of projected basin‐scale decreases in total dissolved solids loads as a result of salinity control efforts. Decreasing trends in baseflow dissolved solids loads suggest that salinity mitigation projects, landscape changes, and/or climate are reducing dissolved solids transported to streams through the subsurface. Notably, the pace and extent of decreases in baseflow dissolved solids loads declined during the most recent decade; average decreasing loads during the 2000s (28,200 mT) were only 54% of average decreasing loads in the 1990s (51,700 mT).