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Samples of the bones of 47 individuals from 46 Czech and Moravian ossuaries were dated by the 14C method and analyzed for the collagen isotopic composition of carbon (δ13C) and nitrogen (δ15N). Most of the data for the ages of the remains corresponded to the cooler and damper periods described over the past 1000 years. Of the studied samples, the greatest number of remains corresponded to the Spörer (1400–1570), Dalton (1790–1830) and Wolf minima (1280–1350). One sample studied falls within the Maunder minimum (1645–1715). It can be assumed that these minima are connected with a reduced production of food and fodder, that may have initiated famines, epidemics and armed conflicts. Individual climatic minima showed positive correlations between δ13C and δ15N values, indicating that the individuals studied consumed complementary plant or animal diets to different degrees. The elevated δ15N values in our studied samples compared to the skeletal compositions of the population of the La Tène period (380 – 150 BC) and Germanic inhabitants in the territory of Bohemia (5th–6th centuries AD) and Great Moravia (9th–early 10th centuries AD) might reflect the effect of greater consumption of animal proteins or the proteins of omnivorous animals and fish, which compensated for the lack of plant foodstuffs during the colder periods.
The isotopic composition of carbon and nitrogen of the bone collagen for the Spörer and Dalton minima differs from the Wolf minimum. The younger minima show higher δ15N values for a given δ13C value.
We start by examining the current composition of the atmosphere, and then turn our attention to some of the most important chemical reactions that take place in the unpolluted atmosphere. In particular, we will introduce you to the hydroxyl radical, nature’s garbage collector. As well as the three well-known greenhouse gases, the IPCC refers to a wide range of other substances as Short-Lived Climate Forcers, including chemically reactive gases such as methane, ozone, nitrogen oxides, carbon monoxide, etc., and aerosols. The atmospheric fate of all these species needs to be understood. After that, we will examine the polluted atmosphere, particularly smog and acid rain. While this topic might not seem directly related to climate change, there are some useful lessons to be learned. We also include a short discussion on how we use isotope data to help narrow in on some of the more important processes in our environment.
Chlorite and illite are commonly associated with ubiquitous secondary K-rich feldspar in the rocks located immediately above and below the Precambrian-Paleozoic unconformity in southwestern Ontario, and elsewhere in the mid-continent of North America. This alteration assemblage is attributed to long-distance migration of hot brines driven westward by orogenic processes originating along the eastern seaboard of North America. The δD and δ18O values of chlorite and illite, plus K-Ar dates for secondary K-rich feldspar and illite, were used to determine the nature, origin, and timing of the fluids that altered Precambrian granites and their overlying rocks in southwestern Ontario. The δ18O values of the chlorite-forming fluids are best explained by initial hot brines (≥50°C) evolved mostly from seawater. Secondary K-rich feldspar formation followed shortly thereafter, as the fluids cooled and perhaps mixed with meteoric water. Regional migration of the brines was induced by Taconic orogenic events to the east. The hydrogen and oxygen isotopic compositions for the secondary illite of the early to mid-Carboniferous indicate its crystallization from local meteoric water at low temperatures (40–55°C). Infiltration of local meteoric water into the Paleozoic and uppermost altered Precambrian rocks occurred during uplift, erosion, and subaerial exposure of local arches in southern Ontario. The local basement reactivation and associated secondary illite formation in this portion of the North American hinterland was likely a distal expression of east-coast Acadian and Alleghanian orogenic activity.
Talc deposits, located mainly in three areas of north-central Turkey, are present in the ophiolitic series of the Cretaceous and in siliciclastic rocks of the Paleocene. Talc deposits related to ophiolites are between tectonite and cumulate occurring as beds and/or lenses and 0.1–3 cm thick fracture fillings within a 5 m brecciated zone with a vein-type bedding. Sedimentary-hosted talc beds and semi-rounded to angular talc grains (0.1–2 cm) range in thickness from 0.1 to 30 cm within marls and conglomerates. Talc veins form lenses (a few meters long) and spheroidal and/or ellipsoidal nodules (1–10 cm). Calcite, dolomite, serpentine and/or mixed-layered illite-smectite (I-S) minerals are encountered in the talc samples. Serpentine with positive U and Hf anomalies, and talc with positive Nb and Zr anomalies, and negative Ta and Ce anomalies are typically depleted in P and Ti, based on chondrite-normalized trace element patterns. The light rare earth element content of sedimentary-hosted talc with a negative Gd anomaly is richer than those of ultramafic-hosted talc with a negative anomaly for Eu as well as serpentine. Significantly, talc with a uniquely sedimentary origin tends to be the principal source of Nb, Hf, Zr, La, Ce, Pr and Nd with respect to serpentine. δ18O and δD values for talc range from +13.8 to +17.5‰ and −60 to −36‰, and those of serpentine are +9.4 and −88‰, indicating supergene conditions for sedimentary-hosted talc and hypogene for ultramafic-hosted talc. When compared with seawater, δ18O data indicate temperatures of 68°C and 80–98°C for the sedimentary- and ultramafic-hosted talc formations, respectively, and 100°C for serpentine, suggesting that talcification and serpentinization of ultramafic rocks both occurred at nearly the same time with various stages. All data show that the talc occurrences are divided into two types based on their mode of formation. The first corresponds to a serpentinization stage within the ophiolites. The others are the neoformation products of sedimentary deposition, diagenetic and post-diagenetic processes, respectively. Sedimentary-hosted talc also seems to have inherited trace element and isotopic compositions from the parent ultramafic rocks.
The clay minerals formed in chilled margins and massive crystallized inner parts of three basalt-hawaiite bodies of Mururoa Atoll (French Polynesia) exhibit contrasting textures. Glass alteration textures are observed around fractures crosscutting the quenched margins: Fe-rich clays grow inward into the glass (retreating surface) while Mg-rich clays grow outward (open space). The textures of clay deposits filling the diktytaxitic voids (mesostasis) in the massive inner parts of the three volcanic bodies are different: unoriented clay matrix with embedded euhedral apatite and pyroxene microcrysts (submarine flow); pallisadic clays coating the void walls and the crystal surfaces of apatite and K-feldspar microcrysts (subaerial flow); and clay muffs covering all the apatite needles, with the central part of the void remaining empty (dike). The unoriented texture could result from the alteration of a glass precursor concomitant with the olivine phenocrysts (clay pseudomorphs). However, such an alteration implies important chemical transfers which are not observed. The pallisadic and muff textures form through heterogeneous nucleation on the solid surfaces and crystal growth from a saline solution. No glass precursor existed. As the center of the diktytaxitic voids in the dike is empty, the residual liquid was probably boiling. The amounts of light rare earth elements (LREE), Sr, and the most incompatible elements are greater in clays from diktytaxitic voids relative to the amounts formed in the altered glass of the chilled margins. Thus, diktytaxitic clays formed from a residual liquid which gave either an evolved glass or a saline solution after cooling (fractionation process). The δ18O variation vs. loss on ignition (LOI) indicates that sea water was involved either in rock alteration or magma contamination. This is confirmed by the 87Rb/86Sr ratio of bulk rocks and clay fractions from the quenched and massive inner parts of the three volcanic bodies which do not fit with the 11.5 Ma isochron indicating that the Rb-Sr system was not closed at any stage during the magmatic history.
Most previous studies of the kaolin deposits in the southeastern United States have focused on their mineralogy and petrology to understand better the depositional and diagenetic environments of the kaolins. Many studies suggest, however, that much of the information held within the minerals was changed during extensive post-depositional groundwater and microbial alteration. Organic δ13C and biomarker analyses were used, therefore, to provide further information on the nature of the original sediments, the depositional environment(s), and the amount of diagenetic alteration that has occurred in Georgia kaolin deposits.
Two different types of kaolin can be discerned, based on their total organic carbon contents: organic-lean kaolin and lignitic kaolin. The bulk organic δ13C in the Georgia kaolins ranges from ~−26 to −19% (VPDB, Vienna Pee Dee Belemnite standard), with a noticeable enrichment in 13C with decrease in organic carbon concentration. The lean kaolins are by far the more dominant types, with an organic-matter composition primarily of C16–C22n-alkanes, C16 and C18 fatty acids, and unresolved complex mixtures. Lignitic kaolin has a distinctly different organic matter (OM) composition. The lignitic material is primarily C15–C33n-alkanes with a greater abundance of C23–C31n-alkanes and lesser amounts of resinous and microbial constituents along with the oxidized forms of the saturated lipid fractions.
Biomarker data suggest that the lignitic material is primarily terrestrially derived from conifers with minor input from microbial lipids. The OM in both types of kaolin shows strong signs of microbial decomposition that yield the organically lean kaolins. The oxidation of the detrital organic matter would subsequently yield organic acids that would have exerted significant influence on the mineralogy and metal mobility.
Differences in equilibration rates among crystals of different sizes may be used to deduce paleofluid changes over time if the crystal-growth mechanism is known. To explore isotopic equilibration rates as a function of illite growth, we studied B-isotope changes during illitization of smectite. Montmorillonite (<2.0 µm SWy-1, K saturated) was reacted with aqueous boric acid (1000 ppm B) at 300°C, 100 MPa in sealed Au capsules (1:1 fluid:mineral ratio). The initial fluid was 0‰ (NBS 951 standard) but after R1 ordering occurred (65 days of reaction) the fluid was changed to −7‰ in order to examine the rate of isotopic re-equilibration. Samples were taken intermittently throughout the experiment. Each aliquot was NH4 exchanged and size separated into fine (<0.2 µm), medium (0.2–2.0 µm) and coarse (>2.0 µm) fractions. The isotopic composition of B in the tetrahedral sheet was then measured for comparison with the predicted equilibrium values.
The fine fraction showed equilibrium isotope ratios within 10 days, indicating that small, newly nucleated crystals precipitate in equilibrium with the fluid under supersaturated, closed conditions. These fine-fraction minerals did not re-equilibrate when the fluid was changed. The medium fraction gradually equilibrated with the initial fluid as illite grew to values >50%, but did not re-equilibrate with the later fluid. The coarse fraction was slow to begin recrystallization, perhaps due to dissolution kinetics of large crystals or the presence of detrital contaminants. However, it showed the fastest rate of isotopic change with crystal growth after R1 ordering. We conclude that at 300°C, the initial B–O bonds formed in illite are stable, and isotopic re-equilibration only occurs on new crystal growth. Therefore, different isotope ratios are preserved in different crystal size fractions due to different rates of crystal growth. Large crystals may reflect equilibrium with recent fluid while smaller crystals may retain isotope compositions reflecting equilibrium with earlier fluids.
The isotope values of fossil snail shells can be important archives of climate. Here, we present the first carbon (δ13C) and oxygen (δ18O) isotope values of snail shells in interior Alaska to explore changes in vegetation and humidity through the late-glacial period. Snail shell δ13C values were relatively consistent through the late glacial. However, late-glacial shell δ13C values are 2.8‰ higher than those of modern shells. This offset is best explained by the Suess effect and changes in the δ13C values of snail diet. Snail shell δ18O values varied through the late glacial, which can be partially explained by changes in relative humidity (RH). RH during the snail growing period was modeled based on a published flux balance model. Results suggest a dry period toward the beginning of the Bølling–Allerød (~14 ka) followed by two distinct stages of the Younger Dryas, a wetter stage in the early Younger Dryas from 12.9 to 12.3 ka, and subsequent drier stage in the late Younger Dryas between 12.3 and 11.7 ka. The results show that land snail isotopes in high-latitude regions may be used as a supplementary paleoclimate proxy to help clarify complex climate histories, such as those of interior Alaska during the Younger Dryas.
The excavation of a palaeochannel at the Vistre de la Fontaine 2-2 archaeological site, 3 km downstream from the ancient city of Nîmes (southeastern France), provided an accumulation sequence covering the last 2,500 years. Trace metal analyses of these alluvial sediments disclosed lead (Pb) contamination during the Early Roman Empire, with concentrations close to 1,000 ppm, a factor of 100 above the local geochemical background. This excess of Pb shows a uniform isotopic signature that may reflect unchanged ore sources, perhaps from the Massif Central or from Great Britain. The Pb peak accompanied visible waste that was transported in the sediments of the Vistre de la Fontaine at the time of the development of the Nîmes urban water supply and drainage network during the Early Roman Empire. This research shows the bimillennial persistence of palaeo-contamination in a peri-urban alluvial plain and the relevance of fluvial sedimentary archives in documenting ancient waste.
This chapter presents a discussion and derivation of the ideal gas law, starting with atoms and molecules. Collisions are characterized by the impulse, the change in momentum due to the collision, determined by the product of the average force during and the time duration of a collision. A free atom or molecule in a box is used to develop the concept of pressure on a wall and, ultimately, the ideal gas law for many noninteracting molecules. The distinction between gauge pressure and absolute pressure is necessary to understand before applying the gas laws. The root mean square (rms) speed for a typical molecule is estimated to be a bit faster than the speed of sound. That is, the molecules can be expected to be supersonic. Included is a discussion of isotopes and carbon dating and their connection to the musical scale.
We evaluate carbonate gastropod shells as 14C proxies for groundwater discharge at springs. Groundwater 14C is commonly used to estimate groundwater transit times, and a carbonate shell proxy would present a different way of collecting groundwater 14C data. Specifically, we test the hypothesis that in exclusively groundwater-fed spring systems, water 14C is preserved in carbonate shells at multiple sites, species, and water 14C. We first present isotopic and water temperature variability over several years at three spring sites in Utah. We then compare the 14C of contemporaneously collected water, sediment, and shells of benthic gastropods (Melanoides tuberculata, Pyrgulopsis pilsbryana, and Physella gyrina). We show that water and shell 14C activities at each site are correlated (slope = 1.00, R2 = 0.999, n = 22). These results support the hypothesis that 14C from groundwater is preserved in carbonate shells, and that aqueous gastropods a viable groundwater 14C proxy. Finally, we describe the utility and limitations of using gastropod shells as a groundwater 14C proxy.
Metal isotope tracers (e.g., 87Sr/86Sr, 7Li/6Li; 138Ba/134Ba) are being employed worldwide to understand downhole processes and assess the environmental impact of hydraulic fracturing. These isotope signatures can be much more sensitive than geochemical tracers alone in discriminating between contaminant sources. This can be particularly useful when time has elapsed after an event and a contaminant has been substantially diluted, or in being able to quickly detect the intrusion of a brine with high total dissolved solids (TDS) into a protected water resource. In some cases, such as areas with multiple sources of water contaminants and overlapping chemical signatures, a multi-proxy approach is recommended. The combination of element ratio and isotopic tracers (e.g. Sr/Ca and 87Sr/86Sr) or multi-isotope tracers (e.g., 87Sr/86Sr and d7Li) can be used to discriminate between multiple contaminant sources and provide important information about the processes involved in concentrating, mobilizing or retaining a contaminant.
During the first millennium ad, Europe saw much socio-environmental change, which is reflected in the archaeological and palaeoecological evidence. Using published and new isotope data from across western Europe, the author examines changing resource use from c.ad 350 to 1200. The geographical limits of millet and substantial marine consumption are identified and comparisons between childhood and adult diets made across regions. Cross-cultural interaction at a broad scale is emphasized and patterns within early medieval England form the subject of an in-depth case study. While doubt is cast onto the uptake of marine resource consumption in England following the Fish Event Horizon, changes in agricultural practices, the impact of Christianization, and the role of freshwater fish in diets are explored. The author's hierarchical meta-analytical approach enables identification of human–environment interactions, with significant implications for changing foodways in Europe during the first millennium ad.
Studies of Sr isotopic composition of thousands of samples of marine sediments and fossils have yielded a curve of 87Sr/86Sr versus age for seawater Sr that extends back to 1 billion years. The ratio has fluctuated with large amplitude during this time period, and because the ratio is always uniform in the oceans globally at any one time, it is useful as a stratigraphic correlation and age-dating tool. The ratio also appears to reflect major tectonic and climatic events in Earth history and hence provides clues as to the causes, timing, and consequences of those events. The seawater 87Sr/86Sr ratio is generally high during periods marked by continent-continent collisions, and lower when continental topography is subdued, and seafloor generation rates are high. There is evidence that major shifts in the seawater ratio can be ascribed to specific orogenic events and correlate with large shifts in global climate.
Fractionation factors for the isotopes of O, H, S, or Cu (as appropriate) were determined for the minerals brochantite [Cu4(SO4)(OH)6], libethenite [Cu2(PO4)(OH)] and olivenite [Cu2(AsO4)(OH)] and corresponding aqueous solutions at temperatures between 30 and 70°C. All samples used for this determination were synthetic and the degree of fractionation was expressed as 1000 ln α = (A × 106/T2) + B, where A and B are empirical parameters. A few natural libethenite samples from its type locality Ľubietová-Podlipa were also analysed and compared to the prediction based on the isotopic composition of meteoric water and our fractionation factors. The hydrogen fractionation factors agreed with the prediction well, whereas those for oxygen did not. A possible explanation is the disequilibrium of aqueous phosphate (and also arsenate) species and the solution in our experiments or the interaction of meteoric fluids with the isotopically heavy (in terms of oxygen) country rocks. Because the effects of isotopic disequilibrium in our experiments cannot be ruled out, the oxygen fractionation factors should be used with caution. The determined fractionation factors can be used as an isotope geothermometer, given that it can be proven that the phases of interest precipitated from the same fluid in equilibrium. Libethenite is predicted to have slightly lower δ65Cu values than its parental solution, but brochantite slightly higher δ65Cu values than its parental solution. Simple forward models, simulating neutralisation or reduction of mine drainage, show that precipitation of these minerals and removal of the co-existing fluid, could cause isotopic variations (in δ65Cu) on the order of 1‰ or more.
Molybdenum (Mo) is a widely used trace metal for investigating redox conditions. However, unanswered questions remain that concentration and bulk isotopic analysis cannot specially answer. Improvements can be made by combining new geochemical techniques to traditional methods of Mo analysis. In this Element, we propose a refinement of Mo geochemistry within aquatic systems, ancient rocks, and modern sediments through molecular geochemistry (systematically combining concentration, isotope ratio, elemental mapping, and speciation analyses). Specifically, to intermediate sulfide concentrations governing Mo behavior below the 'switch-point' and dominant sequestration pathways in low oxygen conditions. The aim of this work is to 1) aid and improve the breadth of Mo paleoproxy interpretations by considering Mo speciation and 2) address outstanding research gaps concerning Mo systematics (cycling, partitioning, sequestration, etc.). The Mo paleoproxy has potential to solve ever complex research questions. By using molecular geochemical recommendations, improved Mo paleoproxy interpretations and reconstruction can be achieved.
The Quaternary Isotope Laboratory (QIL) at the University of Washington was launched in 1969 and directed by Minze Stuiver until his retirement in 1998. Here we review some of the scientific work undertaken in the QIL and the memories of some of Minze’s former students and colleagues.
Augusto Moreno is credited with establishing the first radiocarbon (14C) laboratory in Mexico in the 1950s, however, 14C measurement with the accelerator mass spectrometry (AMS) technique was not achieved in our country until 2003. Douglas Donahue from the University of Arizona, a pioneer in using AMS for 14C dating, participated in that experiment; then, the idea of establishing a 14C AMS laboratory evolved into a feasible project. This was finally reached in 2013, thanks to the technological developments in AMS and sample preparation with automated equipment, and the backing and support of the National Autonomous University of Mexico and the National Council for Science and Technology. The Mexican AMS Laboratory, LEMA, with a compact 1 MV system from High Voltage Engineering Europa, and its sample preparation laboratories with IonPlus automated graphitization equipment, is now a reality.
The chapter is concerned with Kuhnian revolutions in the way that they were originally conceived and also according to Kuhn’s later writings. In particular I analyze a recent proposal by Brad Wray that the switch from using atomic weight to order the elements, to using atomic number, represents a Kuhnian revolution either in the original and classic sense or in terms of a change in the scientific lexicon. The chapter also considers how the literature on the dual sense of the term ‘element’ bears on this discussion and the manner in which the discovery of isotopes of chemical elements were accommodated into the periodic table. Finally, Kuhn’s no overlap principle is examined. This is first carried out in the context in which Kuhn introduced the principle, to characterize how the meaning of the term planet changed in the course of the Copernican revolution. The no overlap principle is then applied to the change in the meaning of the term element which took place during Wray’s proposed atomic number revolution. I argue that the two historical cases are not analogous and that the element case cannot therefore be considered as a revolution in Kuhn’s revised lexical sense.
We examined whether change in added sugar intake is associated with change in δ13C, a novel sugar biomarker, in thirty-nine children aged 5–10 years selected from a Colorado (USA) prospective cohort of children at increased risk for type 1 diabetes. Reported added sugar intake via FFQ and δ13C in erythrocytes were measured at two time points a median of 2 years apart. Change in added sugar intake was associated with change in the δ13C biomarker, where for every 1-g increase in added sugar intake between the two time points, there was an increase in δ13C of 0⋅0082 (P = 0⋅0053), independent of change in HbA1c and δ15N. The δ13C biomarker may be used as a measure of compliance in an intervention study of children under the age of 10 years who are at increased risk for type 1 diabetes, in which the goal was to reduce dietary sugar intake.