A MIS 3 charcoal and pollen record and quantitative precipitation inferences from the Jingerwa section of the Nihewan Basin,north-central China

Pollen and charcoal data from the Jingerwa section of the Nihewan Basin, north-central China, were used to reconstruct vegetation and climate changes during Marine Isotope Stage (MIS) 3. Mean annual precipitation changes were quantified by applying pollen-climate transfer functions. Sparse vegetation cover dominated by herbs indicates relatively dry climate between 51 and 43 cal ka BP. Between 43 and 35 cal ka BP, a Pinus-dominated forest reached its maximum extent, implying that climate was wetter than today. Severe fire episodes during that period suggest warm temperatures. Between 35 and 32 cal ka BP, forest retreat and the expansion of dryland vegetation are indicative of drier climates. Slightly wetter conditions prevailed between 32 and 29 cal ka BP, as indicated by the expansion of ferns. Our results suggest that the climate conditions in the Nihewan Basin during middle and late MIS 3 were probably wetter than today. This may have been caused by intensification of Asian monsoon circulation in response to greater insolation in June at 30°N. However, increases in summer temperatures and evaporation, triggered by peak summer insolation levels, may have led to a reduction in humidity around 35 cal ka BP.     

Investigation of the geochemical impact of CO2 on shallow groundwater: design and implementation of a CO2 injection test in Northeast Germany

A small scale and temporally limited CO₂ injection test was performed in a shallow aquifer to investigate the geochemical impact of CO₂ upon such aquifers and to apply and verify different monitoring methods. Detailed site investigation coupled with multiphase simulations were necessary to design the injection experiment and to set up the monitoring network, before CO₂ was injected over a ten-day period at three injection wells, at a depth of 18?m below surface level into a quaternary sand aquifer located close to the town of Wittstock in Northeast Germany. Monitoring methods comprised groundwater sampling and standard analyses, as well as trace element analyses and isotope analyses; geoelectrical borehole monitoring; passive samplers to analyse temporally integrated for cations and multi-parameter probes that can measure continuously for dissolved CO₂, pH and electrical conductivity. Due to CO₂ injection, total inorganic carbon concentrations increased and pH decreased down to a level of 5.1. Associated reactions comprised the release of major cations and trace elements. Geoelectrical monitoring, as well as isotope analyses and multi-parameter probes proved to be suitable methods for monitoring injected CO₂ and/or the alteration of groundwater.     

Recently induced anoxia leading to the preservation of seasonal laminae in two NE-German lakes

The recent sediments of two lakes in the NE German lowland became seasonally laminated at different times. Anoxic bottom conditions resulted from a surplus of organic matter (OM), in the early stage indicated by irregularly laminated sediments comprising abundant iron-sulfide framboids. Their diagenetic formation predates the preservation of biochemical calcite varves. In the larger, deeper Lake Tiefer See near Klocksin, anoxia developed stepwise. A first anoxic pulse was contemporary with inflow narrowing by railway-dam construction and accumulation of OM. It was favored by a decrease of the intensity of lake circulation (turnover). Nutrients introduced from artificial fertilizer then increased the primary production (diatoms) to the point of OM surplus and seasonal laminae formation started 40 years later in 1924. In the smaller, shallower Lake Tiefer See in the Uckermark, a massive pulse of iron sulfide was centered around 1960, seven years after installation of piped field drainage into the lake. Anoxia developed rapidly with the nutrients drained from a fertilized groundwater catchment that is 10 times larger than the surface catchment, while surface erosion was reduced. Reducing bottom conditions became regular and the seasonal lamination was preserved after 1967. Morphological criteria to screen lakes for varved sediments should include reductions of natural lake inflow and catchment increase, such as by inflow of field drainage. Similar developments of increased nutrient input or intensity decrease of lake circulation may result from historical human activities but also from natural processes.     

Thermodynamic properties and stability of AlF-bearing titanite CaTiOSiO4–CaAlFSiO4

Calorimetric and experimental data on AlF-bearing titanite are presented that yield thermodynamic properties of CaAlFSiO₄, as well as activity-composition relations of binary titanite CaTiOSiO₄-CaAlFSiO₄. The heat capacity of synthetic CaAlFSiO₄ was measured with differential scanning calorimetry between 170 and 850 K: C_P=689.96-0.38647T+2911300T^-2-8356.1T^-0.5+0.00016179T² Based on low-temperature heat capacity calculations with lattice vibrational theory (Debye model), the calorimetric entropy of CaAlFSiO₄ can be expected to lie between 104.7 and 118.1 J mol^-1 K^-1. The temperature of the P2₁/a to A2/a phase change was determined calorimetrically for a titanite with X_Al=0.09 (T_transition=390 K). The decrease of the transition temperature at a rate of about 11 K per mol% CaAlFSiO₄ is in good agreement with previous TEM investigations. The displacement of the reaction anorthite + fluorite = CaAlFSiO₄ in the presence of CaTiOSiO₄ was studied with high P-T experiments. Titanite behaves as a non-ideal, symmetrical solid-solution. The thermodynamic properties of CaAlFSiO₄ consistent with a multi-site mixing model are: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2Daebbnrfi % fHhDYfgasaacH8srps0lbbf9q8WrFfeuY-Hhbbf9v8qqaqFr0xc9pk % 0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qqQ8frFve9 % Fve9Ff0dmeaabaqaciaacaGaaeqabaWaaeaaeaaakeaafaqaaiWaca % aabaGaeeyrauKaeeOBa4MaeeiDaqNaeeiAaGMaeeyyaeMaeeiBaWMa % eeiCaaNaeeyEaKNaeeiiaaIaee4Ba8MaeeOzayMaeeiiaaIaeeOzay % Maee4Ba8MaeeOCaiNaeeyBa0MaeeyyaeMaeeiDaqNaeeyAaKMaee4B % a8MaeeOBa4MaeeiiaaIaeeikaGIaeeyzauMaeeiBaWMaeeyzauMaee % yBa0MaeeyzauMaeeOBa4MaeeiDaqNaee4CamNaeeykaKIaeeiiaaIa % emizaq2aaSbaaSqaaiabdAgaMbqabaGccqWGibasdaahaaWcbeqaai % abicdaWaaaaOqaaiabg2da9iabgkHiTiabikdaYiabiEda3iabisda % 0iabicdaWiabc6caUiabiIda4iabgglaXkabiodaZiabc6caUiabic % daWiabbccaGiabbUgaRjabbQeakjabb2gaTjabb+gaVjabbYgaSnaa % CaaaleqabaGaeyOeI0IaeGymaedaaaGcbaGaee4uamLaeeiDaqNaee % yyaeMaeeOBa4MaeeizaqMaeeyyaeMaeeOCaiNaeeizaqMaeeiiaaIa % ee4CamNaeeiDaqNaeeyyaeMaeeiDaqNaeeyzauMaeeiiaaIaeeyzau % MaeeOBa4MaeeiDaqNaeeOCaiNaee4Ba8MaeeiCaaNaeeyEaKNaeeii % aaIaee4uam1aaWbaaSqabeaacqqGWaamaaaakeaacqqG9aqpcqqGXa % qmcqqGWaamcqqG0aancqqGUaGlcqqG5aqocqGHXcqScqqGXaqmcqqG % UaGlcqqGXaqmcqqGGaaicqqGkbGscqqGTbqBcqqGVbWBcqqGSbaBda % ahaaWcbeqaaiabgkHiTiabigdaXaaakiabbUealnaaCaaaleqabaGa % eyOeI0IaeGymaedaaaGcbaGaeeyta0KaeeyyaeMaeeOCaiNaee4zaC % MaeeyDauNaeeiBaWMaeeyzauMaee4CamNaeeiiaaIaeeiCaaNaeeyy % aeMaeeOCaiNaeeyyaeMaeeyBa0MaeeyzauMaeeiDaqNaeeyzauMaee % OCaiNaeeiiaaYaamWaaeaacqWGxbWvdaWgaaWcbaGaemisaG0aaWba % aWqabeaacqGHsislaaaaleqaaOGaeeivaqLaem4vaC1aaSbaaSqaai % abdohaZbqabaaakiaawUfacaGLDbaaaeaacqGH9aqpcqaIXaqmcqaI % ZaWmcqGGUaGlcqaI2aGncqGHXcqScqaIWaamcqGGUaGlcqaI0aanca % aMe8UaeeOsaOKaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqGH % sislcqaIXaqmaaaaaaaa!E403!

Quantitative relationship between water-depth and sub-fossil ostracod assemblages in Lake Donggi Cona,Qinghai Province,China

A calibration data set of 51 surface sediment samples from Lake Donggi Cona on the northeastern Tibetan Plateau was investigated to study the relationship between sub-fossil ostracod assemblages and water depth. Samples were collected over a depth range from 0.6 to 80 m. A total of 16 ostracod species was identified from the lake with about half of the species restricted to the Tibetan Plateau and its adjacent mountain ranges and poorly known in terms of ecological preferences, and the other half displaying a mainly Holarctic distribution. Living macrophytes and macroalgae were recorded in Lake Donggi Cona down to a depth of about 30 m, and bivalve (Pisidium cf. zugmayeri) and gastropod (Gyraulus, Radix) shells were found down to depths of 43 and 48 m, respectively. The ostracod-water-depth relationship was assessed by multivariate statistical analysis and ostracod-based transfer functions for water depth were constructed. Weighted averaging partial least squares (WA-PLS) regression provided the best model with a coefficient of determination r ² of 0.91 between measured and ostracod-inferred water depth, a root mean square error of prediction of 8% and a maximum bias of 10.6% of the gradient length, as assessed by leave-one-out cross-validation. Our results show the potential of ostracods as palaeo-depth indicators in appropriate settings. However, transfer-function applications using fossil ostracod assemblages for palaeo-depth estimations require a thorough understanding of the palaeolimnological conditions of lakes and therefore detailed multi-proxy analysis to avoid misinterpretation of ostracod-based inferences.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

Using variations in the stable carbon isotope composition of macrophyte remains to quantify nutrient dynamics in lakes

The apparent isotope enrichment factor ε_macrophyte of submerged plants (ε_{macrophyte–DIC} = δ¹³C_macrophyte − δ¹³C_DIC) is indicative of dissolved inorganic carbon (DIC) supply in neutral to alkaline waters and is related to variations in aquatic productivity (Papadimitriou et al. in Limnol Oceanogr 50:1084–1095, 2005). This paper aims to evaluate the usage of ε_macrophyte inferred from isotopic analyses of submerged plant fossils in addition to analyses of lake carbonate as a palaeolimnological proxy for former HCO₃ ⁻ concentrations. Stable carbon isotopic analysis of modern Potamogeton pectinatus leaves and its host water DIC from the Tibetan Plateau and Central Yakutia (Russia) yielded values between −23.3 and +0.4‰ and between +14.0 and +6.5‰, respectively. Values of ε _{Potamogeton–DIC} (range −15.4 to +1.1‰) from these lakes are significantly correlated with host water HCO₃ ⁻ concentration (range 78–2,200 mg/l) (r = −0.86; P < 0.001), thus allowing for the development of a transfer function. Palaeo-ε _{Potamogeton–ostracods} values from Luanhaizi Lake on the NE Tibetan Plateau, as inferred from the stable carbon isotope measurement of fossil Potamogeton pectinatus seeds (range −24 to +2.8‰) and ostracods (range −7.8 to +7.5%) range between −14.8 and 1.6‰. Phases of assumed disequilibrium between δ¹³C_DIC and δ¹³C_ostracods known to occur in charophyte swards (as indicated by the deposition of charophyte fossils) were excluded from the analysis of palaeo-ε. The application of the ε _{Potamogeton–DIC}-HCO₃ ⁻ transfer function yielded a median palaeo-HCO₃ ⁻ -concentration of 290 mg/l. Variations in the dissolved organic carbon supply compare well with aquatic plant productivity changes and lake level variability as inferred from a multiproxy study of the same record including analyses of plant macrofossils, ostracods, carbonate and organic content.     

Suitability of Mn‐ and Fe‐Rich Reference Materials for Microanalytical Research

Manganese‐ and iron‐rich materials are of major geoscientific and economic interest, many of which contain microscopic features that provide valuable information. To obtain accurate results, a homogeneous microanalytical reference material for calibration is needed. Several researchers have used the Mn‐ and Fe‐rich RMs, JMn‐1, NOD‐A‐1, NOD‐P‐1 and FeMn‐1, for this purpose; therefore, they were tested in this study to determine their suitability for microanalysis. Their homogeneity was investigated by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) with two different types of lasers (nano‐ and femtosecond), with spot and line scan analyses and with different operating parameters, such as spot size, pulse repetition rate and fluence. As the established manganese nodule RMs revealed inhomogeneities for picogram to microgram test portions, we also investigated the new synthetic Fe‐ and Mn‐rich RM, FeMnOx‐1. FeMnOx‐1 was found to be homogeneous for large (ø 40 μm: 2% RSD repeatability) and small (ø 8–10 μm: 10% RSD repeatability) spot sizes. This homogeneity is in the range of the homogeneous NIST SRM 610 and GSE‐1G reference glasses. Furthermore, FeMnOx‐1 revealed a large‐scale homogeneity within uncertainties of a few per cent, using test portions in the ng range, when measuring four individual mounts of this material.