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Tonsteins, predominantly solid kaolinite clay interbeds, are widespread in the coals of the Kuznetsk Basin and usually contain idiomorphic zircon grains of magmatic origin in quantities suitable for uranium-lead (U-Pb) radiometric dating. For the first time, tonstein zircons from coal seam 78 of the Tailugan Formation (Fm) are dated by two methods: Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Chemical Abrasion Isotope-Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS).The CA-ID-TIMS datings of 257.0 ± 1.3 Ma and 256.6 ± 0.4 Ma determine the age of the lower boundary of the Tailugan Fm and the Tailuganian Regional Stage at 257.0 Ma. We estimate the duration of the Tailuganian to be around 4.22 million years. The dating results make it possible to directly correlate the Tailuganian of the Kuzbass with the upper half of the Wuchiapingian and with most of the Changhsingian of the International Chronostratigraphic Scale.The accumulation rate of total sediments of the Tailugan Fm, calculated without considering the compaction index, is approximately 0.13–0.18 mm/year, and the rate of coal accumulation is 0.024 mm/year. Such values are comparable to the accumulation rates of the Late Paleozoic coal-bearing strata of the Donetsk Basin and Western Australia. The rate of peat accumulation during the Tailuganian, calculated at a compaction index of 10:1, has been estimated at 0.24 mm/year. This value is comparable to the rates of peat accumulation in the Holocene bogs of the Kuznetsk Alatau in Siberia and the European part of Russia.The presence of tonsteins in the coal seams of the Tailugan Fm suggests that the upper surface of the peat at the time of its accumulation was below the water level, serving as a protective screen for the thin volcanic deposits and preventing its erosion.The assemblages of macroflora, ostracods, conchostracans and bivalves considerably vary through the section of the Tailugan Fm. This variation makes it possible to identify in Kuzbass the stratigraphic level that corresponds to the boundary between the Wuchiapingian and Changhsingian stages in the future.

This article discusses the Late Kungurian radioisotopic age (276.9 ± 0.4 Ma) of the middle part of the Starokuznetsk Formation (Kuznetsk Subgroup, Kolchugino Group) of the Kuznetsk Basin determined by chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS). The analysis of the biostratigraphic data confirms that the layer dated belongs to the interval in which the Balakhonka Flora (cordaitoid) was replaced by the Kolchugino Flora (fern-pteridosperm-cordaitoid). This indicates that the change from the Balakhonka Flora to the Kolchugino Flora in the low latitudes of Angaraland took place during the Late Kungurian. The data obtained were used for direct correlation of the lower part of the Kolchugino Group with the Upper Kungurian of the International Chronostratigraphic Chart. Similar sequences of non-marine bivalve assemblages in the Permian successions of Angaraland (giant Prokopievskia, Khosedaella-Redikorella-Palaeomutela, and dominant Palaeomutela) and Eastern Europe (giant Sinomya, Palaeomutela-Khosedaella-Redikorella, and dominant Palaeomutela) further support the validity of the correlation of the Kuznetsk Subgroup with the Ufimian Stage. The placement of the lower boundary of the Kolchugino Group in the upper part of the Kungurian Stage of the International Chronostratigraphic Scale raises the question of the continuation of the Ufimian Stage as an independent straton in the East European Stratigraphic Scale. Its lower boundary coincides with the beginning of the change in the Balakhonka and Kolchugino Flora in the low latitudes of Angaraland, as well as with the faunal exchanges between the Euramerican and Angarian non-marine bivalve assemblages.

The German capital Berlin originates from the two medieval settlements Berlin and Cölln on either side of the river Spree. Whereas Berlin is world famous, there is very little awareness of former Cölln. From 2007-2009, during excavations of the earliest cemetery of this forgotten medieval town; 3,126 graves were discovered containing the remains of 3,717 individuals. Amongst those graves was an unusual triple burial. This grave was exceptional due to the relative postures of the skeletons and their extensive facial injuries. Here we present genetic and isotope data for this grave. Genetic results confirmed all of them as biological male individuals and ruled out their biological kinship. Combining genetic ancestry information with strontium isotope data we furthermore determined that two of the men most likely originated from the Berlin-Brandenburg region, whereas a more distant origin of the third individual can be debated., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Rationale: Identifying migratory corridors of animals is essential for their effective protection, yet the exact location of such corridors is often unknown, particularly for elusive animals such as bats. While migrating along the German coastline, Nathusius' pipistrelles (Pipistrellus nathusii) are regularly killed at wind turbines. Therefore, we explored the paths taken on their annual journey., Methods: We used isotope ratio mass spectrometry to measure stable hydrogen and strontium isotope ratios in fur keratin of 59 Nathusius' pipistrelles captured on three offshore islands. Samples were pre-treated before analysis to report exclusively stable isotope ratios of non-exchangeable hydrogen. We generated maps to predict summer origins of bats using isoscape models., Results: Bats were classified as long-distance migrants, mostly originating from Eastern Europe. Hydrogen analysis suggested for some bats a possible Fennoscandian origin, yet additional information from strontium analysis excluded this possibility. Instead, our data suggest that most Nathusius' pipistrelles migrating along the German coastline were of continental European summer origin, but also highlight the possibility that Nathusius' pipistrelles of Baltorussian origin may travel offshore from Fennoscandia to Germany., Conclusions: Our findings demonstrate the benefit of using complementary isotopic tracers for analysing the migratory pathways of bats and also potentially other terrestrial vertebrate species. Furthermore, data from our study suggest an offset of fur strontium isotope ratios in relation to local bedrock., (© 2020 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.)

The isotope composition of dissolved sulphate and strontium in atmospheric deposition, groundwater, mine water and river water in the region of Freiberg was investigated to better understand the fate of these components in the regional and global water cycle. Most of the isotope variations of dissolved sulphates in atmospheric deposition from three locations sampled bi- or tri-monthly can be explained by fractionation processes leading to lower [Formula: see text] (of about 2-3‰) and higher [Formula: see text] (of about 8-10‰) values in summer compared with the winter period. These samples showed a negative correlation between [Formula: see text] and [Formula: see text] values and a weak positive correlation between [Formula: see text] and [Formula: see text] values. They reflect the sulphate formed by aqueous oxidation from long-range transport in clouds. However, these isotope variations were superimposed by changes of the dominating atmospheric sulphate source. At two of the sampling points, large variations of mean annual [Formula: see text] values from atmospheric bulk deposition were recorded. From 2008 to 2009, the mean annual [Formula: see text] value increased by about 5‰; and decreased by about 4‰ from 2009 to 2010. A change in the dominating sulphate source or oxidation pathways of SO(2) in the atmosphere is proposed to cause these shifts. No changes were found in corresponding [Formula: see text] values. Groundwater, river water and some mine waters (where groundwater was the dominating sulphate source) also showed temporal shifts in their [Formula: see text] values corresponding to those of bulk atmospheric deposition, albeit to a lower degree. The mean transit time of atmospheric sulphur through the soil into the groundwater and river water was less than a year and therefore much shorter than previously suggested. Mining activities of about 800 years in the Freiberg region may have led to large subsurface areas with an enhanced groundwater flow along fractures and mined-refilled ore lodes which may shorten transit times of sulphate from precipitation through groundwater into river water.

Batch experiments with the lead sulphide ore mineral galena were carried out in order to get information about the oxidation mechanisms and to contribute to the understanding of field data, especially those obtained from the mining-affected sites. Results indicate that oxygen and sulphur isotopes of dissolved sulphate may be useful tools for the investigation of galena oxidation mechanisms. However, some methodological modifications are necessary to obtain sufficient sulphate yields, which are a prerequisite for the reduction of the analytical uncertainty. Surface and hydrochemical investigations indicated that galena was dissolved non-oxidatively during the experiment at initial pH 2, whereas the oxidative dissolution of galena dominated in experiments at initial pH 6 and 8. No isotope results could be obtained from the experiment at initial pH 2 due to the low sulphate production. The oxidative dissolution of galena resulted in somewhat higher sulphate yields. Thus, the oxygen isotope composition of sulphate produced from galena oxidation could be determined for the first time. Oxygen in sulphate derived largely from water molecules; but minor amounts of molecular oxygen could be also observed. Both molecular oxygen and ferric iron may act as oxidants of galena. A variety of intermediate reactions allow for a variable oxygen isotope composition of sulphate. Sulphur isotopes of sulphate showed an enrichment of (32)S in sulphate (relative to galena), which increases with increasing pH. Sulphur isotope enrichment processes may be associated with the formation of anglesite.

Pituitary adenomas are one of the most frequent intracranial tumors with a prevalence of clinically-apparent tumors close to 1:1000 of the general population. They are clinically significant because of hormone overproduction and/or tumor mass effects in addition to the need for neurosurgery, medical therapies and radiotherapy. The majority of pituitary adenomas have a sporadic origin with recognized genetic mutations seldom being found; somatotropinomas are an exception, presenting frequent somatic GNAS mutations. In this and other phenotypes, tumorigenesis could possibly be explained by altered function of genes implicated in cell cycle regulation, growth factors or their receptors, cell-signaling pathways, specific hormonal factors or other molecules with still unclear mechanisms of action. Genetic changes, such as allelic loss or gene amplification, and epigenetic changes, usually by promoter methylation, have been implicated in abnormal gene expression, but alternative mechanisms may be present. Familial cases of pituitary adenomas represent 5% of all pituitary tumors. MEN1 mutations cause multiple endocrine neoplasia type 1 (MEN1), while the Carney complex (CNC) is characterized by mutations in the protein kinase A regulatory subunit-1alpha (PRKAR1A) gene or changes in a locus at 2p16. Recently, a MEN1-like condition, MEN4, was found to be related to mutations in the CDKN1B gene. The clinical entity of familial isolated pituitary adenomas (FIPA) is characterized by genetic defects in the aryl hydrocarbon receptor interacting protein (AIP) gene in about 15% of all kindreds and 50% of homogenous somatotropinoma families. Identification of familial cases of pituitary adenomas is important as these tumors may be more aggressive than their sporadic counterparts., (Copyright 2010 Elsevier Ltd. All rights reserved.)

Oxidation experiments with different pyrite grain sizes (63-100, 100-140, 140-180 microm) were carried out to investigate the oxygen and sulphur isotope composition of sulphate produced under aerobic acid conditions, which may help to understand oxidation mechanisms and to interpret data from natural sites. Long-term experiments with grain size 63-100 microm showed that constant delta (18)O(SO4) values were not achieved before 100 days. The final oxygen isotope difference between water and sulphate indicates that a small proportion of molecular oxygen is incorporated into sulphate even in the later course of the oxidation due to sulphite oxidation by molecular oxygen. However, most of the sulphate oxygen derives from water. Similar delta (18)O(SO4) values from experiments with grain sizes 63-100, 100-140, and 140-180 microm indicate similar oxidation mechanisms for all three grain sizes. These results differed from previous results of identical experiments with grain size<63 microm, where higher delta (18)O(SO4) values were obtained. We propose that the greater proportion of molecular oxygen in sulphate from oxidised fine-grained pyrite is caused by an intensified adsorption of molecular oxygen on sulphur sites of ultrafine pyrite particles. Hence, the formation of sulphate from the (initial) reaction on sulphur sites of pyrite and from sulphite oxidation should be more dominant if ultrafine material is present. The delta (34)S(SO4) values (2.0-2.7) obtained from experiments with the coarser grain sizes agreed with the delta (34)S value of pyrite (2.4), whereas sulphur isotopes of sulphate obtained from previous experiments with fine-grained pyrite showed an initial (32)S enrichment compared with pyrite. Due to the lack of delta (34)S(SO4) values from the beginning of the experiments with coarser grain sizes, it remains speculative that sulphur isotopes indicate at least initial differences in oxidation mechanisms between fine and coarser pyrite grain sizes.

Objective: Mutations in the aryl hydrocarbon receptor-interacting protein (AIP) were recently shown to confer a pituitary adenoma predisposition in patients with familial isolated pituitary adenomas (FIPA). We report a large Samoan FIPA kindred from Australia/New Zealand with an R271W mutation that was associated with aggressive pituitary tumors., Design and Methods: Case series with germline screening of AIP and haplotype analyses among R271W families., Results: This previously unreported kindred consisted of three affected individuals that either presented with or had first symptoms of a pituitary macroadenoma in late childhood or adolescence. The index case, a 15-year-old male with incipient gigantism and his maternal aunt, had somatotropinomas, and the maternal uncle of the index case had a prolactinoma. All tumors were large (15, 40, and 60 mm maximum diameter) and two required transcranial surgery and radiotherapy. All three affected subjects and ten other unaffected relatives were found to be positive for a germline R271W AIP mutation. Comparison of the single nucleotide polymorphism patterns among this family and two previously reported European FIPA families with the same R271W mutation demonstrated no common ancestry., Conclusions: This kindred exemplifies the aggressive features of pituitary adenomas associated with AIP mutations, while genetic analyses among three R271W FIPA families indicate that R271W represents a mutational hotspot that should be studied further in functional studies.

Familial pituitary adenomas are found in multitumoral syndromes such as multiple endocrine neoplasia type 1 (NEM1) and type 4 (NEM4) and the Carney complex (CNC); it remains at present the only known condition in the category of familial isolated pituitary adenomas (FIPA). Familial adenomas account for 3-5% of all pituitary adenomas. Their pathogenesis is known in part: mutations of the menin gene in NEM1 (80%), of the CDKN1B gene in NEM4 (several cases described), of the PRKR1A gene in CNC (50%) and the AIP gene in 15% of FIPA cases (50% of the FIPA cases with a homogeneous somatotropic phenotype). The clinical course of familial adenoma with NEM1 or FIPA is more aggressive than that of sporadic adenoma, with more macroadenomas and more patients diagnosed younger. Familial pituitary adenomas are distinguished from the sporadic forms in their genetic, epidemiologic and clinical characteristics. They require a differentiated management, especially concerning screening.

To pinpoint the origin and mixing processes of mine waters, different mine water types from the polymetallic sulphide ore deposit 'Himmelfahrt Fundgrube' (Freiberg, Germany) were analysed by thermal ionisation mass spectrometry using lead and strontium isotope ratios. Results show that the lead isotope composition of different mine waters results from a mixture of at least two sources: released lead from oxidised sulphide ores (mainly galena) and anthropogenic lead from groundwater. Furthermore, there are indications for an additional lead source. Strontium isotopes in mine waters identify at least three different sources: released strontium from weathered host rock (Grey Gneisses), released strontium from weathered gangue carbonates, and probably strontium from anthropogenic inputs. Contrary to former oxygen and sulphur isotope studies, strontium isotope compositions as well as hydrochemical parameters show the important role of gangue carbonates as an element source in mine waters.

The isotopic composition of air-borne sulphur was investigated in Saxony, Southeast Germany--a region with formerly very high atmospheric SO(2) concentrations. In addition, data from various authors were compiled for different Saxonian locations, spanning from 1992 to 2004, i.e., a time of decreasing SO(2) concentrations in the atmosphere. There were no obvious temporal changes in the mean delta(34)S value of bulk precipitation. However, the variability of monthly mean delta(34)S values decreased. The mean sulphur isotope composition of sulphate from bulk precipitation after the year 2000 converges in Saxony towards 4-5 per thousand, with similar values for different locations. Mean values of different forms of sulphur show the following enrichment order: delta(34)S of SO(2) < delta(34)S of weathering crusts < or =delta(34)S of sulphate from bulk precipitation < or =delta(34)S of dust. Judging from local differences on sulphate crusts and corresponding isotope values of sources, the delta(34)S value of SO(2) as well as for crusts mainly reflects local point sources. The mean delta(34)S value of bulk precipitation represents more regionally well-mixed SO(2) sources and is therefore an ideal tool for monitoring regional atmospheric change.

Elemental analyzer/continuous flow isotope ratio mass spectrometry (EA/CF-IRMS) has become a standard procedure for the determination of delta(34)S values. Common procedures are, however, frequently less than satisfactory for organic as well as for mineral samples with very low concentrations of sulfur (<2000 ppm). Here we present a method which employs cold trapping of SO(2) to adjust the gas concentration for subsequent isotope signature determination. Analytical accuracy is comparable with common EA/CF-IRMS analysis without trapping, showing a precision of better than +/-0.4 per thousand in delta(34)S (1 SD). The virtual absence of memory effects was established by analyzing adjacent samples exhibiting a large difference in delta(34)S and by prolonged freezing of the carrier gas, yielding virtually no S concentration peak. The method was tested using less than 15% (6 microg) of the S required for a conventional isotope analysis at comparable signal intensity. Even smaller samples can be analyzed with high precision. This facilitates the on-line delta(34)S determination in small biological and mineral samples, minimizing matrix effects in various materials including sandstone, soil, and plant samples., (Copyright (c) 2006 John Wiley & Sons, Ltd.)

Members of the Toll receptor (Tlr) family have a crucial role in the innate immune response following bacterial infection. The effects of Gram-negative bacteria-derived endotoxins (lipopolysaccharide, LPS) are predominantly mediated by Tlr4, and we have recently shown that pituitary folliculostellate cells express functional Tlr4. In the present study, we investigated whether Tlr4 is also present in normal and transformed endocrine epithelial pituitary cell types. By reverse transcriptase-polymerase chain reaction, Tlr4 mRNA expression was found in some pituitary epithelial tumour cell lines (AtT20, HP75), whereas others were negative (GH3, alphaT3-1). Tlr4 protein was detected by immunohistochemistry in a few epithelial cells in normal human anterior pituitaries and in 26 out of 67 human pituitary tumours analysed. LPS had no effect on adrenocorticotropic hormone secretion in Tlr4-positive AtT20 cells, but it suppressed the growth of these cells in a dose-dependent manner. As expected, neither hormone secretion, nor growth of Tlr4-negative GH3 cells was affected by LPS. In cell cultures of Tlr4-positive pituitary adenomas, LPS dose-dependently stimulated the production of interleukin (IL)-6, which is known to induce growth and hormone production in pituitary tumours. The LPS-induced IL-6 production was blocked by the specific p38alphaMAP kinase inhibitor, SB203580, and by the synthetic glucocorticoid, dexamethasone. The data suggest that, during Gram-negative bacteria-induced infections or inflammatory processes, LPS could affect pituitary tumour pathophysiology and progression in the subset of Tlr4-expressing pituitary adenomas.

As an enzyme implicated in the stress response, we investigated poly(ADP-ribose) polymerase (PARP) in the response of GH3 rat pituitary tumor cells to oxidants. These cells are unusual in that they undergo rapid cell death (90 min) with low doses of the prooxidant, H2O2 (50-200 microm), whereas at higher doses (1 mm), death occurs some hours later (4-5 h). Measurement of PARP activity shows that low doses of H2O2 (50-200 microm) fail to increase the activity of PARP, whereas at 0.5 and 1 mm, the enzyme becomes activated. In parallel with the activation of PARP, cellular ATP concentrations fall at high H2O2 doses and the PARP inhibitors, 3-aminobenzamide and nicotinamide (NIC) partially prevent this fall. Using NIC to inhibit PARP activity, we show that treatment of cells with NIC before the addition of H2O2 (0.5-1 mm), results in rapid cell death (90 min). In contrast, prior exposure to H2O2 (0.5-1 mm) for 1 h, before withdrawal and exposure to 1 mm NIC, allows cell survival for many hours. These data suggest that PARP is involved in blocking rapid death of GH3 cells in response to oxidants. In contrast to other cell types tested here, in which inhibitor studies show that PARP is activated at low H2O2 doses and this decreases the extent of apoptosis, GH3 cells are unable to sufficiently activate PARP to prevent rapid cell death.

We investigated physical, chemical and isotope (S, O) parameters of sulfate from acid mine drainage from the polymetallic sulfide ore deposit Freiberg (Gennany), which was mined for more than eight hundred years. Two main groups of water were distinguished: 1. Flowing mine water with sulfate concentrations of less than 9,000 mg/l and pH values higher than 3.2, 2. Pore water in weathered low grade ores and pools with sulfate concentrations higher than 9000mg/l and pH values below 3.2. The sulfur and oxygen isotope composition of sulfate from flowing mine waters reflects mixing of sulfate from two sulfur sources: a) atmospheric sulfur from precipitation and b) sulfate formed as a result of sulfide oxidation processes. Sulfur isotope values of mine water sulfate were used to estimate the contribution of sulfate derived through oxidation of sulfides. The sulfur isotope composition of pore water sulfate and precipitated sulfate (jarosite) from weathered low grade ore samples is identical to the sulfur isotope composition of primary sulfides. The oxygen isotope composition of pore water sulfate from low grade ore samples indicates that the oxidation process proceeds relatively slowly in 02-depleted waters, probably without significant microbial catalysis.