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The application of Ca isotopic analysis in biomedical studies has great potential to identify changes in Ca metabolism and bone metabolism. Reliable measurement of Ca isotope-amount ratios is challenging considering limited Ca amounts and significant procedural blank levels. In this study, Ca purification was performed using the DGA Resin, optimized for low procedural blanks and separation of Ca from matrix elements and isobaric interferences (Na, Mg, K, Ti, Fe, Ba), while maintaining quasi-quantitative recoveries which are sufficient since a 42Ca–48Ca double-spike (DS) was applied. Ca isotopic analysis was performed using multicollector thermal ionization mass spectrometry (MC TIMS). The obtained procedural Ca blank of ≤10 ng enables processing of limited Ca amounts down to 670 ng. Data reduction of the measured Ca isotope-amount ratios was performed using an in-house developed software solving the DS algorithm. Data quality was improved by extension of equilibration time of the sample-DS mixture and implementation of a normalization strategy for raw isotopic data. The reported δ(44Ca/40Ca)NIST SRM 915a of NIST SRM 915a processed as a sample was found to be 0.01 ‰ ± 0.08 ‰ (2 SD, n = 15). Ca isotope-amount ratios of the reference material NIST SRM 1400 (bone ash), NIST SRM 1486 (bone meal), GBW07601 (human hair), and IAPSO (seawater) were in good agreement within uncertainty with literature data. Novel data on additional reference materials for biological tissues (hair) is presented, which might indicate a potential fractionation of Ca incorporated into hair tissue when compared to the blood pool.

Ca isotopes have gained increasing interest as a diagnostic tool for bone diseases due to the variations in abundances as a consequence of changes in bone-mineral balance. Optimized Ca/matrix separation prior to analysis is a prerequisite for reliable isotope ratio measurements in complex biological matrices such as blood, serum, or urine. The online analysis of analyte/matrix separation by ICP-MS enables direct assessment of elution profiles supporting the optimization process. The integration of transient signals and signal suppression challenge the quantification and interpretation of the elution profiles. Mn and Co remain unretained by the DGA Resin (TrisKem International) from nitric acid. Hence, in the present study, these elements were investigated for their application as standards to monitor signal suppression. Successful analyte quantification was accomplished using a dynamic correction strategy applying a linear gradient of a suppression factor based on Mn and Co intensities. An optimized Ca/matrix separation procedure using DGA Resin is proposed based on the results during online ICP-MS analysis. Graphic abstract

The potential of enriched Pb (

The Upper Palaeolithic double burial of newborns and the single burial of a ca. 3-month-old infant uncovered at the Gravettian site of Krems-Wachtberg, Austria, are of paramount importance given the rarity of immature human remains from this time. Genome-wide ancient DNA shows that the male infants of the double grave are the earliest reported case of monozygotic twins, while the single grave´s individual was their 3rd-degree male relative. We assessed the individuals´ age at death by applying histological and µCT inspection of the maxillary second incisors (i2) in conjunction with C- and N-isotope ratios and Barium (Ba) intake as biomarker for breastfeeding. The results show that the twins were full-term newborns, and that while individual 2 died at birth, individual 1 survived for about 50 days. The findings show that Gravettian mortuary behaviour also included re-opening of a grave and manipulation of its layout and content., Maria Teschler-Nicola et al. use ancient DNA sequencing to report the earliest known case of human monozygotic twins found in a previously discovered Upper Palaeolithic burial site. Using bioanthropological and archaeological techniques, they also find that the twins were full-term newborns and that ancient mortuary behavior included re-opening of grave sites to bury related individuals together.

Although there are common and well-established bioindicator organisms and tissues, there is still a need for reliable and sensitive bioindicators in aquatic environments. In the present pilot study, calcified structures in fish were applied as indicators of metal exposure in combination with commonly used fish soft tissues and intestinal parasites, therefore comprising short- and long-term indicators. Patterns of metal accumulation and distribution in soft (muscle, liver) and hard (scales, otoliths) tissues of brown trout (Salmo trutta Linnaeus, 1758) and their intestinal parasites, acanthocephalans (Dentitruncus truttae Sinzar, 1955), from the Krka River influenced by industrial and municipal wastewaters were estimated and compared. Most elements had higher levels in acanthocephalans, scales and liver than muscle and otoliths, possibly reflecting differences in metal uptake routes, tissue function and metabolic activity. Despite the recorded differences in metal contents, all applied bioindicators reflected environmental conditions in a similar way, indicating higher levels of most elements in fish from the contaminated rather than from the reference site. Acanthocephalans were confirmed as sensitive bioindicators due to effective metal accumulation capacity, while the combination of soft and hard tissues provided extended temporal information on metal exposure. Wastewater impact was evidenced as moderate metal pollution by all applied indicators and pointed to present but also long-term disturbances in the Krka River and the importance of continuous monitoring and protective actions.

The environmental fate of the frequently used broad-spectrum β-lactam antibiotic amoxicillin (AMX) is of high concern regarding the potential evolution of antimicrobial resistance (AMR). Moreover, it is known that AMX is prone to hydrolysis, yielding a variety of hydrolysis products (HPs) with yet unknown effects. Studies to identify those HPs and investigate their formation mechanisms have been reported but a long-term study on their stability in real water samples was missing. In this regard, we investigated the hydrolysis of AMX at two concentration levels in four distinct water types under three different storage conditions over two months. Concentrations of AMX and four relevant HPs were monitored by an LC-MS/MS method revealing pronounced differences in the hydrolysis rate of AMX in tap water and mineral water on the one hand (fast) and surface water on the other (slow). In this context, the occurrence, relative intensities, and stability of certain HPs are more dependent on the water type than on the storage condition. As clarified by ICP-MS, the main difference between the water types was the content of the metals copper and zinc which are supposed to catalyze AMX hydrolysis demonstrating an effective method to degrade AMX at ambient conditions.

Objectives: Since the late 1970s, when the first human skeletal remains from a pit (V1141) located within the Late Bronze Age hillfort at Stillfried an der March, Austria, were discovered, their deviation from the predominant burial rite of cremation became the subject-matter of a variety of archaeological and bioanthropological studies. Through continuous archaeological excavations, further settlement pits with unusual human inhumation burials or depositions of isolated skeletal remains became apparent and posed the question of their possible non-local origin. The human samples in this study come from the Pits V841 and V1133, furthermore we re-investigate two individuals from V1141. The aim is to get a better understanding of Stillfried’s population structure and to enrich the debate about the mortuary practices of the Urnfield culture. Material and Methods: Here we present and discuss the radiogenic Sr isotope ratios determined in the enamel of eleven individuals from three settlement pits: eight individuals from Pit V841 and one individual, represented by a skull without mandible (calvarium) of a 12–13-year-old child from Pit V1133; two individuals were taken from Pit V1141 and re-investigated for comparative reasons. We compared all data to signals of the local environment derived from modern environmental samples and to the autochthonous signal of the Late Bronze Age derived from archaeological faunal remains (incl. mussels) and archaeological plants. Further, we investigated and discussed the potential of a mathematical approach to access biogenic Sr isotopic information from diagenetically altered dentine. Results: It has been shown that both supposedly autochthonous and allochthonous (non-local) individuals are buried within the settlement pits of Stillfried, which shows that burial practices do not relate to the individual’s origins. In particular, the n(87Sr)/n(86Sr) isotopic values of six individuals match the supposedly autochthonous Sr signature, while the other five individuals represent allochthonous individuals. Three of the latter showed n(87Sr)/n(86Sr) values that were higher and two that were lower compared to the autochthonous Sr range, thereby indicating at least two different homelands. Despite the small sample size which constrains the validity of the data, the diversity of the inhabitants’ provenance reflects a high mobility. This may support the interpretation of Stillfried as a ‘central site’ – a finding which is also important in the wider context of the European Late Bronze Age.

Sr isotopes were applied to identify possible allochthony of skeletal remains retrieved from Tomb 26 of the pharaonic cemetery SAC5 on Sai Island (Nubia). Tooth enamel of nine individuals, including the Overseer of Goldsmiths Khummose and his presumed ‘wife’, dating from the New Kingdom, were investigated to gain information whether these individuals were first generation immigrants from Egypt (= allochthonous) or members of the local population inhabiting the area of Sai Island (= autochthonous). The interpretation of supposed allochthony and autochthony was based on the comparison of the Sr of human enamel to an assumed autochthonous Sr isotopic composition. The autochthonous Sr signal on Sai Island during the New Kingdom was derived from archaeological animal samples (rodent, sheep/goat, dog and local mollusc shells dating from the New Kingdom) in combination with local environmental samples (paleo sediments dating from the New Kingdom and literature Sr isotope value of Nile River water for the New Kingdom era). As the Sr values in enamel of all individuals investigated lay within the determined autochthonous Sr range on Sai Island during the New Kingdom, all individuals were classified as supposed members of the local population on Sai Island. Elevated Sr, V, Mn and U mass fractions indicated a high degree of post-mortem alterations of human primary dentine. Hence, a mathematical approach was tested in order to correct the Sr isotope ratios in human primary dentine for diagenetic alteration considering a diagenetic Sr proportion and the Sr isotopic composition of the repository material. The rich funerary equipment associated with the burials in Tomb 26 allowed a dating of the family members of Khnummose and illustrated that they belonged to the Egyptian elite on Sai Island as far as their cultural identity is concerned. In combination with the Sr isotopic analysis, Tomb 26 provided fresh information on the complex coexistence and biological and cultural entanglement of Egyptians and Nubians on Sai Island during the New Kingdom.

Copper-based fungicides have been used for a long time in viticulture and have accumulated in many vineyard soils. In this study, incrementing Cu(OH)2-based fungicide application from 0.05 to 5 g Cu kg−1 on two agricultural soils (an acidic sandy loam (L, pH 4.95) and an alkaline silt loam (D, pH 7.45)) resulted in 5 times more mobile Cu in the acidic soil. The most sensitive parameters of alfalfa (Medicago sativa) growing in these soils were the root nodule number, decreasing to 34% and 15% of the control at 0.1 g Cu kg−1 in soil L and at 1.5 g Cu kg−1 in soil D, respectively, as well as the nodule biomass, decreasing to 25% and 27% at 0.5 g Cu kg−1 in soil L and at 1.5 g Cu kg−1 in soil D, respectively. However, the enzymatic N2-fixation was not directly affected by Cu in spite of the presence of Cu in the meristem and the zone of effective N2-fixation, as illustrated by chemical imaging. The strongly different responses observed in the two tested soils reflect the higher buffering capacity of the alkaline silt loam and showed that Cu mitigation and remediation strategies should especially target vineyards with acidic, sandy soils.

The focus of this study was to assess the potential of otolith microchemistry as a fishery management tool for different European freshwater fish species in an Alpine foreland with a diverse range of different water bodies but low geological variation. 87Sr/86Sr isotope and Sr/Ca ratios in water samples from 26 habitat sites in a pre-alpine catchment region around lake Chiemsee, Germany, an important region for recreational and economic fisheries, were analysed. 87Sr/86Sr isotope ratios and the Sr mass fractions in otoliths of 246 fish out of 16 species were determined using (laser ablation) inductively coupled plasma mass spectrometry ((LA)-ICP-MS). Habitats could be discriminated into three distinct strontium isotope regions (SIGs) and seven clusters with characteristic 87Sr/86Sr isotope and Sr/Ca ratios. The direct comparison of 87Sr/86Sr isotope ratios in water and otolith samples allowed to identify fish that might have been a) migrating b) transferred from other water bodies or c) stocked from fish farms. Sr/Ca ratios in water and the Sr mass fraction in otoliths were highly correlated, although significant differences between species from the same environment could be documented. Sr mass fractions in sagittae of Perca fluviatilis were about 60 % of those in sagittae of Coregonus spp and of lapilli of roach Rutilus rutilus from the same habitats. Different partition factors for water to otolith Sr/Ca mass fractions were determined for different species. Discrimination of fish otoliths by 87Sr/86Sr isotope ratios and Sr mass fractions according to habitat clusters was possible with success rates ranging from 92 % to 100 % for cyprinids, European perch Perca fluviatilis, whitefish Coregonus spp. and European grayling Thymallus thymallus, and was 74 % for salmonids. Otolith microchemistry proved to have great potential to serve as a fishery management tool at smaller spatial scales such as in the studied Alpine foreland when considering the limited variation of 87Sr/86Sr isotope and Sr/Ca ratios, the type and spatial distribution of habitats, and the species and question under investigation.HighlightsOtolith microchemistry applied in in area with limited geological variabilityFish transferred, stocked or migrated were identifiedRegressions between Sr/Ca ratios in water predict Sr mass fractions in otolithsSpecies specific Sr discrimination from water into otolithsEuropean freshwater fish species assigned to habitat clusters of origin

This paper presents a systematic investigation of the effects of Ca on the matrix separation of Sr and Pb and subsequent isotope-amount ratio measurements using a variety of synthetic solutions and reference materials with varying Ca content during the application of an automated analyte/matrix separation approach. The separation method based on the DGA resin was optimized by using increased column bed volumes, comparing two different column sizes (1-mL and 3-mL-bed volume). Certified reference materials (synthetic calcium carbonate – MACS-3, basalt – BCR-2, saggital otolith – FEBS-1, bone meal – NIST SRM 1486, bone ash – NIST SRM 1400, and skim milk powder – BCR-063R) with varying Ca content, Ca/Sr and Ca/Pb mass fraction ratios were separated using the optimized method and analyzed for the Sr and Pb isotopic composition by multi collector inductively coupled plasma mass spectrometry (MC ICP-MS). The developed separation method based on the 3-mL-bed volume column provides quantitative recoveries (84% to 105% for Sr, 77 % to 96% for Pb), while maintaining a quantitative separation of Sr and Pb. Procedural blank levels were

This paper presents a combination of elemental and isotopic spatial distribution imaging with near-infrared hyperspectral imaging (NIR-HSI) to evaluate the diagenetic status of skeletal remains. The aim is to assess how areas with biogenic n(87Sr)/n(86Sr) isotope-amount ratios may be identified in bone material, an important recorder complementary to teeth. Elemental (C, P, Ca, Sr) and isotopic (n(87Sr)/n(86Sr)) imaging were accomplished via laser ablation (LA) coupled in a split stream to a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS) and a multicollector inductively coupled plasma mass spectrometer (MC ICP-MS) (abbreviation for the combined method LASS ICP-QMS/MC ICP-MS). Biogenic areas on the bone cross section, which remained unaltered by diagenetic processes, were localized using chemical indicators (I(C)/I(Ca) and I(C) × 10/I(P) intensity ratios) and NIR-HSI at a wavelength of 1410 nm to identify preserved collagen. The n(87Sr)/n(86Sr) isotope signature analyzed in these areas was in agreement with the biogenic bulk signal revealed by solubility profiling used as an independent method for validation. Elevated C intensities in the outer rim of the bone, caused by either precipitated secondary minerals or adsorbed humic materials, could be identified as indication for diagenetic alteration. These areas also show a different n(87Sr)/n(86Sr) isotopic composition. Therefore, the combination of NIR-HSI and LASS ICP-QMS/MC ICP-MS allows for the determination of preserved biogenic n(87Sr)/n(86Sr) isotope-amount ratios, if the original biogenic material has not been entirely replaced by diagenetic material.

A novel, fast and reliable sample preparation procedure for the simultaneous separation of Sr, Pb, and Nd has been developed for subsequent isotope ratio analysis of sediment digests. The method applying a fully automated, low-pressure chromatographic system separates all three analytes in a single-stage extraction step using self-packed columns filled with DGA Resin. The fully automated set-up allows the unattended processing of three isotopic systems from one sediment digest every 2 h, offering high sample throughput of up to 12 samples per day and reducing substantially laboratory manpower as compared to conventional manual methods. The developed separation method was validated using the marine sediment GBW-07313 as matrix-matched certified reference material and combines quantitative recoveries (>90% for Sr, >93% for Pb, and >91% for Nd) with low procedural blank levels following the sample separation (0.07 μg L−1 Sr, 0.03 μg L−1 Pb, and 0.57 μg L−1 Nd). The average δ values for Sr, Pb, and Nd of the separated reference standards were within the certified ranges (δ (87Sr/86Sr)NIST SRM 987 of −0.05(28) ‰, δ(208Pb/206Pb)NIST SRM 981 of −0.21(14) ‰, and δ(143Nd/144Nd)JNdi-1 of 0.00(7) ‰). The DGA Resin proved to be reusable for the separation of >10 sediment digests with no significant carry-over or memory effects, as well as no significant on-column fractionation of Sr, Pb, and Nd isotope ratios. Additional spike experiments of NIST SRM 987 with Pb, NIST SRM 981 with Sr, and JNdi-1 with Ce revealed no significant impact on the measured isotopic ratios, caused by potential small analyte peak overlaps during the separation of Sr and Pb, as well as Ce and Nd.