scholarly journals Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

2014 ◽  
Vol 14 (23) ◽  
pp. 31813-31841
Author(s):  
S. J. Allin ◽  
J. C. Laube ◽  
E. Witrant ◽  
J. Kaiser ◽  
E. McKenna ◽  
...  
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Stratospheric Ozone ◽  
Isotope Ratios ◽  
Gas Chromatography Mass Spectrometry ◽  
Chlorine Isotope ◽  
Site Model ◽  
Tropospheric Measurements ◽  
Single Detector

Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are (−2.4 ± 0.5) and (−2.3 ± 0.4)‰ for CFC-11, (−12.2 ± 1.6) and (−6.8 ± 0.8)‰ for CFC-12 and (−3.5 ± 1.5) and (−3.3 ± 1.2)‰ for CFC-113, respectively. Assuming a constant source isotope composition, we estimate the expected trends in the tropospheric isotope signature of these gases due to their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these model results to the long-term δ(37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (NEEM site) and Antarctica (Fletcher Promontory site). Model trends agree with tropospheric measurements within analytical uncertainties. From 1970 to the present-day, we find no evidence for variations in chlorine isotope ratios associated with changes in CFC manufacturing processes. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes, using a single-detector gas chromatography-mass spectrometry system.

scholarly journals Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

2015 ◽  
Vol 15 (12) ◽  
pp. 6867-6877 ◽  
Author(s):  
S. J. Allin ◽  
J. C. Laube ◽  
E. Witrant ◽  
J. Kaiser ◽  
E. McKenna ◽  
...  
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Stratospheric Ozone ◽  
Standard Uncertainty ◽  
Gas Chromatography Mass Spectrometry ◽  
Sources And Sinks ◽  
Chlorine Isotope ◽  
Tropospheric Measurements ◽  
Single Detector

Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.

scholarly journals Identifying vital effects in <i>Halimeda</i> algae with Ca isotopes

2014 ◽  
Vol 11 (24) ◽  
pp. 7207-7217 ◽  
Author(s):  
C. L. Blättler ◽  
S. M. Stanley ◽  
G. M. Henderson ◽  
H. C. Jenkyns
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Test Organism ◽  
Isotope Ratios ◽  
First Order ◽  
Geological Past ◽  
Rayleigh Distillation ◽  
Vital Effects ◽  
Specific Factors ◽  
Biogenic Carbonates

Abstract. Geochemical records of biogenic carbonates provide some of the most valuable records of the geological past, but are often difficult to interpret without a mechanistic understanding of growth processes. In this experimental study, Halimeda algae are used as a test organism to untangle some of the specific factors that influence their skeletal composition, in particular their Ca-isotope composition. Algae were stimulated to precipitate both calcite and aragonite by growth in artificial Cretaceous seawater, resulting in experimental samples with somewhat malformed skeletons. The Ca-isotope fractionation of the algal calcite (−0.6‰) appears to be much smaller than that for the algal aragonite (−1.4‰), similar to the behaviour observed in inorganic precipitates. However, the carbonate from Halimeda has higher Ca-isotope ratios than inorganic forms by approximately 0.25‰, likely because of Rayleigh distillation within the algal intercellular space. In identifying specific vital effects and the magnitude of their influence on Ca-isotope ratios, this study suggests that mineralogy has a first-order control on the marine Ca-isotope cycle.

Hydrogeological responses in tropical mountainous springs

2019 ◽  
Author(s):  
Ricardo Sánchez-Murillo
Keyword(s):  
Costa Rica ◽  
Isotope Composition ◽  
Central Valley ◽  
Distribution Functions ◽  
Geochemical Composition ◽  
Transit Times ◽  
Management Plans ◽  
Best Fit ◽  
Term Data

This study presents a hydrogeochemical analysis of spring responses (2013-2017) in the tropical mountainous region of the Central Valley of Costa Rica. The isotopic distribution of δ18O and δ2H in rainfall resulted in a highly significant meteoric water line: δ2H = 7.93×δ18O + 10.37 (r2=0.97). Rainfall isotope composition exhibited a strong dependent seasonality. The isotopic variation (δ18O) of two springs within the Barva aquifer was simulated using the FlowPC program to determine mean transit times (MTTs). Exponential-piston and dispersion distribution functions provided the best-fit to the observed isotopic composition at Flores and Sacramento springs, respectively. MTTs corresponded to 1.23±0.03 (Sacramento) and 1.42±0.04 (Flores) years. The greater MTT was represented by a homogeneous geochemical composition at Flores, whereas the smaller MTT at Sacramento is reflected in a more variable geochemical response. The results may be used to enhance modelling efforts in central Costa Rica, whereby scarcity of long-term data limits water resources management plans.

scholarly journals UV Stimulated Manganese Dioxide for the Persulfate Catalytic Degradation of Bisphenol A

Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 502
Author(s):  
Guihua Dong ◽  
Bing Chen ◽  
Bo Liu ◽  
Stanislav R. Stoyanov ◽  
Yiqi Cao ◽  
...  
Keyword(s):  
Bisphenol A ◽  
Reaction Mechanisms ◽  
Reduction Rate ◽  
Catalytic Degradation ◽  
Gas Chromatography Mass Spectrometry ◽  
Degradation Pathways ◽  
Industrial Chemicals ◽  
Oh Groups ◽  
Long Term Adverse Effects

One of the most commonly produced industrial chemicals worldwide, bisphenol A (BPA), is used as a precursor in plastics, resins, paints, and many other materials. It has been proved that BPA can cause long-term adverse effects on ecosystems and human health due to its toxicity as an endocrine disruptor. In this study, we developed an integrated MnO2/UV/persulfate (PS) process for use in BPA photocatalytic degradation from water and examined the reaction mechanisms, degradation pathways, and toxicity reduction. Comparative tests using MnO2, PS, UV, UV/MnO2, MnO2/PS, and UV/PS processes were conducted under the same conditions to investigate the mechanism of BPA catalytic degradation by the proposed MnO2/UV/PS process. The best performance was observed in the MnO2/UV/PS process in which BPA was completely removed in 30 min with a reduction rate of over 90% for total organic carbon after 2 h. This process also showed a stable removal efficiency with a large variation of pH levels (3.6 to 10.0). Kinetic analysis suggested that 1O2 and SO4•− played more critical roles than •OH for BPA degradation. Infrared spectra showed that UV irradiation could stimulate the generation of –OH groups on the MnO2 photocatalyst surface, facilitating the PS catalytic degradation of BPA in this process. The degradation pathways were further proposed in five steps, and thirteen intermediates were identified by gas chromatography-mass spectrometry. The acute toxicity was analyzed during the treatment, showing a slight increase (by 3.3%) in the first 30 min and then a decrease by four-fold over 2 h. These findings help elucidate the mechanism and pathways of BPA degradation and provide an effective PS catalytic strategy.

Adipose tissue triglyceride turnover, de novo lipogenesis, and cell proliferation in humans measured with 2H2O

2004 ◽  
Vol 286 (4) ◽  
pp. E577-E588 ◽  
Author(s):  
A. Strawford ◽  
F. Antelo ◽  
M. Christiansen ◽  
M. K. Hellerstein
Keyword(s):  
Cell Proliferation ◽  
Adipose Tissue ◽  
Half Life ◽  
De Novo ◽  
Human Subjects ◽  
De Novo Lipogenesis ◽  
Gas Chromatography Mass Spectrometry ◽  
Distribution Analysis ◽  
Mass Isotopomer Distribution Analysis

The turnover of adipose tissue components (lipids and cells) and the pathways of adipose lipid deposition have been difficult to measure in humans. We apply here a 2H2O long-term labeling technique for concurrent measurement of adipose-triglyceride (TG) turnover, cell (DNA) proliferation, and de novo lipogenesis (DNL). Healthy subjects drank 2H2O (70 ml/day) for 5-9 wk. Subcutaneous adipose tissue aspirates were taken (gluteal, thigh, and flank depots). Deuterium incorporation into TG glycerol (representing all-source TG synthesis), TG palmitate (representing DNL, by mass isotopomer distribution analysis), and DNA (representing cell proliferation) was measured by gas chromatography-mass spectrometry. Subjects tolerated the protocol well, and body 2H2O enrichments were stable. Mean TG-glycerol fractional synthesis was 0.12 (i.e., 12%) with a range of 0.03-0.32 after 5 wk and 0.20 (range 0.08-0.49) after 9 wk (TG half-life 200-270 days). Label decay measurements 5-8 mo after discontinuing 2H2O gave similar turnover estimates. Net lipolysis (TG turnover) was 50-60 g/day. DNL contribution to adipose-TG was 0.04 after 9 wk, representing ∼20% of newly deposited TG. Cell proliferation was 0.10-0.17 after 9 wk (half-life 240-425 days). In summary, long-term 2H2O administration to human subjects allows measurement of the dynamics of adipose tissue components. Turnover of all elements is slow, and DNL contributes ∼20% of new TG.

scholarly journals Reconciling differences in stratospheric ozone composites

2017 ◽  
Vol 17 (20) ◽  
pp. 12269-12302 ◽  
Author(s):  
William T. Ball ◽  
Justin Alsing ◽  
Daniel J. Mortlock ◽  
Eugene V. Rozanov ◽  
Fiona Tummon ◽  
...  
Keyword(s):  
Time Series ◽  
Likelihood Function ◽  
Stratospheric Ozone ◽  
Gaussian Mixture ◽  
Robust Estimate ◽  
Mixture Density ◽  
Source Data ◽  
Ozone Trends ◽  
Decadal Trend

Abstract. Observations of stratospheric ozone from multiple instruments now span three decades; combining these into composite datasets allows long-term ozone trends to be estimated. Recently, several ozone composites have been published, but trends disagree by latitude and altitude, even between composites built upon the same instrument data. We confirm that the main causes of differences in decadal trend estimates lie in (i) steps in the composite time series when the instrument source data changes and (ii) artificial sub-decadal trends in the underlying instrument data. These artefacts introduce features that can alias with regressors in multiple linear regression (MLR) analysis; both can lead to inaccurate trend estimates. Here, we aim to remove these artefacts using Bayesian methods to infer the underlying ozone time series from a set of composites by building a joint-likelihood function using a Gaussian-mixture density to model outliers introduced by data artefacts, together with a data-driven prior on ozone variability that incorporates knowledge of problems during instrument operation. We apply this Bayesian self-calibration approach to stratospheric ozone in 10° bands from 60° S to 60° N and from 46 to 1 hPa (∼ 21–48 km) for 1985–2012. There are two main outcomes: (i) we independently identify and confirm many of the data problems previously identified, but which remain unaccounted for in existing composites; (ii) we construct an ozone composite, with uncertainties, that is free from most of these problems – we call this the BAyeSian Integrated and Consolidated (BASIC) composite. To analyse the new BASIC composite, we use dynamical linear modelling (DLM), which provides a more robust estimate of long-term changes through Bayesian inference than MLR. BASIC and DLM, together, provide a step forward in improving estimates of decadal trends. Our results indicate a significant recovery of ozone since 1998 in the upper stratosphere, of both northern and southern midlatitudes, in all four composites analysed, and particularly in the BASIC composite. The BASIC results also show no hemispheric difference in the recovery at midlatitudes, in contrast to an apparent feature that is present, but not consistent, in the four composites. Our overall conclusion is that it is possible to effectively combine different ozone composites and account for artefacts and drifts, and that this leads to a clear and significant result that upper stratospheric ozone levels have increased since 1998, following an earlier decline.

scholarly journals Long-term UVB exposure promotes predator-inspection behaviour in a fish

2017 ◽  
Vol 13 (12) ◽  
pp. 20170497 ◽  
Author(s):  
Simon Vitt ◽  
Janina E. Zierul ◽  
Theo C. M. Bakker ◽  
Ingolf P. Rick
Keyword(s):  
Gasterosteus Aculeatus ◽  
Stratospheric Ozone ◽  
Ultraviolet B ◽  
Antipredator Behaviour ◽  
Uvb Radiation ◽  
Ecological Processes ◽  
Predator Prey ◽  
Natural Sunlight ◽  
Predator Inspection

Ultraviolet-B radiation (UVB) reaching the earth's surface has increased due to human-caused stratospheric ozone depletion. Whereas the harmful effects of UVB on aquatic organisms are well studied at the molecular and cellular level, recent studies have also begun to address behavioural changes caused by sublethal amounts of UVB. However, the behavioural consequences of long-term exposure to ecologically relevant UVB levels over several life stages are virtually unknown, particularly with regard to predator–prey behaviour. We found increased predator-inspection behaviour together with a smaller body length in three-spined sticklebacks ( Gasterosteus aculeatus ) after fish were exposed for about seven months to natural sunlight conditions with enhanced UVB, compared with full siblings exposed to natural sunlight only. The observed change in antipredator behaviour may reflect a direct behavioural response mediated through UVB-induced oxidative stress during development. Alternatively, the smaller body size in UVB-exposed fish may result in an increased inspection effort allowing them to spend more time foraging. Our findings suggest that, within the scope of environmental change, UVB radiation constitutes an important stress factor by eliciting behavioural responses that influence crucial ecological processes, such as predator–prey interactions.

Pleistocene–Holocene environmental change in the Canary Archipelago as inferred from the stable isotope composition of land snail shells

2011 ◽  
Vol 75 (3) ◽  
pp. 658-669 ◽  
Author(s):  
Yurena Yanes ◽  
Crayton J. Yapp ◽  
Miguel Ibáñez ◽  
María R. Alonso ◽  
Julio De-la-Nuez ◽  
...  
Keyword(s):  
Environmental Change ◽  
Canary Islands ◽  
Environmental Changes ◽  
Isotope Composition ◽  
Moving Average ◽  
Land Snail ◽  
Balance Model ◽  
Low Latitude ◽  
The Times

AbstractThe isotopic composition of land snail shells was analyzed to investigate environmental changes in the eastern Canary Islands (28–29°N) over the last ~ 50 ka. Shell δ13C values range from −8.9‰ to 3.8‰. At various times during the glacial interval (~ 15 to ~ 50 ka), moving average shell δ13C values were 3‰ higher than today, suggesting a larger proportion of C4 plants at those periods. Shell δ18O values range from −1.9‰ to 4.5‰, with moving average δ18O values exhibiting a noisy but long-term increase from 0.1‰ at ~ 50 ka to 1.6–1.8‰ during the LGM (~ 15–22 ka). Subsequently, the moving average δ18O values range from 0.0‰ at ~ 12 ka to 0.9‰ at present. Calculations using a published snail flux balance model for δ18O, constrained by regional temperatures and ocean δ18O values, suggest that relative humidity at the times of snail activity fluctuated but exhibited a long-term decline over the last ~ 50 ka, eventually resulting in the current semiarid conditions of the eastern Canary Islands (consistent with the aridification process in the nearby Sahara). Thus, low-latitude oceanic island land snail shells may be isotopic archives of glacial to interglacial and tropical/subtropical environmental change.

Immigration, Assimilation, and Status in the Ancient City of Teotihuacan: Stable Isotopic Evidence from Tlajinga 33

2004 ◽  
Vol 15 (2) ◽  
pp. 176-198 ◽  
Author(s):  
Christine D. White ◽  
Rebecca Storey ◽  
Fred J. Longstaffe ◽  
Michael W. Spence
Keyword(s):  
Tooth Development ◽  
Stable Carbon Isotope ◽  
Geographic Location ◽  
Isotope Ratios ◽  
Bone Collagen ◽  
Considerable Proportion ◽  
Economic Productivity ◽  
Oxygen Isotope Ratios ◽  
Immigration Assimilation

AbstractStable carbon isotope ratios in bone collagen and oxygen isotope ratios in bone and enamel phosphate from 25 individuals from the residential compound of Tlajinga 33 were used to examine the possibility that the inhabitants, who were craft producers, may have accepted immigrants to maintain either their ability to reproduce themselves as a social group or their level of economic productivity. Bone δ18O and δ13C values provide a long-term picture of geographic identity and diet, and enamel δ18O values provide a snapshot of geographic location during particular tooth development. A considerable proportion (29 percent) of the Tlajinga 33 inhabitants grew up elsewhere, but the majority of these immigrants had dwelt in Teotihuacan for many years before their death. Neither geographical relocation nor dietary differences are significantly associated with gender. The social position of foreigners appears to have been generally high. For example, the occupants of Tomb 50 appear to have come from elsewhere, possibly West Mexico, but foreigners were also found in lower status contexts such as middens. The stable isotope ratios reflecting long-term dwelling at Teotihuacan suggest that social status was achieved, which supports current archaeological evidence. Furthermore, the lack of dietary differences between immigrants and native Teotihuacanos may also imply political and/or ethnic assimilation.

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