Methyl bromide: Ocean sources, ocean sinks, and climate sensitivity

The oceans play an important role in the geochemical cycle of methyl bromide (CH_3Br), the major carrier of O_3-destroying bromine to the stratosphere. The quantity of CH_3Br produced annually in seawater is comparable to the amount entering the atmosphere each year from natural and anthropogenic sources. The production mechanism is unknown but may be biological. Most of this CH_3Br is consumed in situ by hydrolysis or reaction with chloride. The size of the fraction which escapes to the atmosphere is poorly constrained; measurements in seawater and the atmosphere have been used to justify both a large oceanic CH_3Br flux to the atmosphere and a small net ocean sink. Since the consumption reactions are extremely temperature-sensitive, small temperature variations have large effects on the CH_3Br concentration in seawater, and therefore on the exchange between the atmosphere and the ocean. The net CH_3Br flux is also sensitive to variations in the rate of CH_3Br production. We have quantified these effects using a simple steady state mass balance model. When CH_3Br production rates are linearly scaled with seawater chlorophyll content, this model reproduces the latitudinal variations in marine CH_3Br concentrations observed in the east Pacific Ocean by Singh et al. [1983] and by Lobert et al. [1995]. The apparent correlation of CH_3Br production with primary production explains the discrepancies between the two observational studies, strengthening recent suggestions that the open ocean is a small net sink for atmospheric CH_3Br, rather than a large net source. The Southern Ocean is implicated as a possible large net source of CH_3Br to the atmosphere. Since our model indicates that both the direction and magnitude of CH_3Br exchange between the atmosphere and ocean are extremely sensitive to temperature and marine productivity, and since the rate of CH_3Br production in the oceans is comparable to the rate at which this compound is introduced to the atmosphere, even small perturbations to temperature or productivity can modify atmospheric CH_3Br. Therefore atmospheric CH_3Br should be sensitive to climate conditions. Our modeling indicates that climate-induced CH_3Br variations can be larger than those resulting from small (±25%) changes in the anthropogenic source, assuming that this source comprises less than half of all inputs. Future measurements of marine CH_3Br, temperature, and primary production should be combined with such models to determine the relationship between marine biological activity and CH_3Br production. Better understanding of the biological term is especially important to assess the importance of non anthropogenic sources to stratospheric ozone loss and the sensitivity of these sources to global climate change

Adsorption of HO_x on Aerosol Surfaces: Implications for the Atmosphere of Mars

The potential impact of heterogeneous chemistry on the abundance and distribution of HO_x in the atmosphere of Mars has been assessed by combining observational data of dust and ice aerosol distributions with an updated photochemical model. Critical parameters include the altitude distributions of aerosols, and the surface loss coefficients (γ) of HO_2 on dust and ice in the lower atmosphere, and H on ice above 40 km. We find that adsorption of HO_2 on dust (γHO_2 ≥ 0.01), or ice near 30 km (γHO_2 ≥ 0.1), can deplete OH abundances in the lower atmosphere by 10% or more. Such depletions approach those obtained by lowering the water vapor abundance by an order of magnitude below the global average observed by Viking (≈ 25%). Since the oxidation of CO is catalyzed by HO_x in the lower atmosphere via the reaction CO + OH → CO_2 + H, loss of OH due to adsorption of HO_2 on dust or ice at low altitudes could have a significant effect on the ratio CO : CO_2. The adsorption of H on ice at 50 km (γ_H ≥ 0.01) can result in even larger OH depletions. However, this effect is localized to altitudes > 40 km, where CO oxidation is relatively unimportant. Laboratory data suggest that γHO_2 ≈ 0.01 is a reasonable estimate for adsorption on dust. Larger values are plausible, but are not strongly supported by experimental evidence. The reactivity of HO_2 on ice is unknown, while γH on ice appears to be < 0.001. There is a need for measurements of HO_x adsorption on surfaces representative of Martian aerosols at temperatures < 220 K

Self-hypnosis for anxiety associated with severe asthma: a case report

BACKGROUND: Management of asthma can be complicated by both medical and psychiatric conditions, such as gastroesophageal reflux, chronic sinusitis, and anxiety. When symptoms of asthma are interpreted without regard to such conditions treatment may yield a suboptimal outcome. For example, anxiety-associated dyspnea, tachypnea, and chest tightness can be mistakenly interpreted as resulting from an exacerbation of asthma. Medical treatment directed only for asthma may thus lead to overuse of asthma medications and increased hospitalizations. CASE PRESENTATION: The described case illustrates how a systemic steroid-dependent patient with asthma benefited from receiving care from a pediatric pulmonologist who also was well versed in the diagnosis and treatment of anxiety. By using self-hypnosis, the patient was able to reduce her dependence on bronchodilators. Following modification of her medical therapy under supervision of the pulmonologist, and regular use of hypnosis, the patient ultimately was weaned off her systemic steroid therapy. CONCLUSIONS: This report emphasizes that anxiety must be considered as a comorbid condition in the treatment of asthma. Self-hypnosis can be a useful skill in the treatment of a patient with anxiety and asthma

Rhenium in seawater: Confirmation of generally conservative behavior

A depth profile of the concentration of Re was measured in the Pacific Ocean using a technique we have developed for the clean chemical separation and the precise measurement of Re by isotope dilution and negative thermal ionization mass spectrometry (ID-NTIMS). This technique permits Re concentrations to be determined from 200 mL of seawater with a typical precision of ±5‰. This is an improvement of at least a factor of 100 over the techniques used in previously published determinations of Re in seawater. We obtain a narrow range for Re from 7.20 ± 0.03 to 7.38 ± 0.03 ng/kg for depths between 45 m and 4700 m. This demonstrates that Re is relatively well mixed throughout the water column and confirms the theoretical prediction that the behavior of Re in the oceans is conservative. When examined in detail, both salinity and the concentration of Re increase by approximately 1.5% between 400 and 4700 m, a correlation consistent with conservative behavior. However, Re appears to be depleted relative to salinity by 1.0–1.5% at 100 m, and enriched by approximately 4% at the surface. These observations suggest a minor level of Re scavenging in near surface waters, and an input of Re to the ocean surface. This work demonstrates the utility of ID-NTIMS for geochemical investigations of certain trace elements that have not previously been amenable to detailed study

Mercury abundance and isotopic composition indicate subaerial volcanism prior to the end-Archean “whiff” of oxygen

Funding: This study was supported by National Aeronautics and Space Administration Exobiology Grant NNX16AI37G (R.B.) and by the MacArthur Professorship (J.D.B.) at the University of Michigan. M.A.K. acknowledges support from an Agouron Institute postdoctoral fellowship.Earth’s early atmosphere witnessed multiple transient episodes of oxygenation before the Great Oxidation Event 2.4 billion years ago (Ga) [e.g., A. D. Anbar et al., Science 317, 1903–1906 (2007); M. C. Koehler, R. Buick, M. E. Barley, Precambrian Res. 320, 281–290 (2019)], but the triggers for these short-lived events are so far unknown. Here, we use mercury (Hg) abundance and stable isotope composition to investigate atmospheric evolution and its driving mechanisms across the well-studied “whiff” of O2 recorded in the ∼2.5-Ga Mt. McRae Shale from the Pilbara Craton in Western Australia [A. D. Anbar et al., Science 317, 1903–1906 (2007)]. Our data from the oxygenated interval show strong Hg enrichment paired with slightly negative Δ199Hg and near-zero Δ200Hg, suggestive of increased oxidative weathering. In contrast, slightly older beds, which were evidently deposited under an anoxic atmosphere in ferruginous waters [C. T. Reinhard, R. Raiswell, C. Scott, A. D. Anbar, T. W. Lyons, Science 326, 713–716 (2009)], show Hg enrichment coupled with positive Δ199Hg and slightly negative Δ200Hg values. This pattern is consistent with photochemical reactions associated with subaerial volcanism under intense UV radiation. Our results therefore suggest that the whiff of O2 was preceded by subaerial volcanism. The transient interval of O2 accumulation may thus have been triggered by diminished volcanic O2 sinks, followed by enhanced nutrient supply to the ocean from weathering of volcanic rocks causing increased biological productivity.PostprintPeer reviewe

Using Natural Stable Calcium Isotopes to Rapidly Assess Changes in Bone Mineral Balance Using a Bed Rest Model to Induce Bone Loss

Metabolic bone diseases like osteoporosis result from the disruption of normal bone mineral balance (BMB) resulting in bone loss. During spaceflight astronauts lose substantial bone. Bed rest provides an analog to simulate some of the effects of spaceflight; including bone and calcium loss and provides the opportunity to evaluate new methods to monitor BMB in healthy individuals undergoing environmentally induced-bone loss. Previous research showed that natural variations in the Ca isotope ratio occur because bone formation depletes soft tissue of light Ca isotopes while bone resorption releases that isotopically light Ca back into soft tissue (Skulan et al, 2007). Using a bed rest model, we demonstrate that the Ca isotope ratio of urine shifts in a direction consistent with bone loss after just 7 days of bed rest, long before detectable changes in bone mineral density (BMD) occur. The Ca isotope variations tracks changes observed in urinary N-teleopeptide, a bone resorption biomarker. Bone specific alkaline phosphatase, a bone formation biomarker, is unchanged. The established relationship between Ca isotopes and BMB can be used to quantitatively translate the changes in the Ca isotope ratio to changes in BMD using a simple mathematical model. This model predicts that subjects lost 0.25 0.07% ( SD) of their bone mass from day 7 to day 30 of bed rest. Given the rapid signal observed using Ca isotope measurements and the potential to quantitatively assess bone loss; this technique is well suited to study the short-term dynamics of bone metabolism

Rapidly Assessing Changes in Bone Mineral Balance Using Natural Stable Calcium Isotopes

We demonstrate that variations in the Ca isotope ratios in urine rapidly and quantitatively reflect changes in bone mineral balance. This variation occurs because bone formation depletes soft tissue of light Ca isotopes, while bone resorption releases that isotopically light Ca back into soft tissue. In a study of 12 individuals confined to bed rest, a condition known to induce bone resorption, we show that Ca isotope ratios shift in a direction consistent with net bone loss after just 7 days, long before detectible changes in bone density occur. Consistent with this interpretation, the Ca isotope variations track changes observed in N-teleopeptide, a bone resorption biomarker, while bone-specific alkaline phosphatase, a bone formation biomarker, is unchanged. Ca isotopes can in principle be used to quantify net changes in bone mass. Ca isotopes indicate an average loss of 0.62 +/- 0.16 % in bone mass over the course of this 30-day study. The Ca isotope technique should accelerate the pace of discovery of new treatments for bone disease and provide novel insights into the dynamics of bone metabolism

An Archean Biosphere Initiative

The search for life on extrasolar planets will necessarily focus on the imprints of biolgy on the composition of planetary atmospheres. The most notable biological imprint on the modern terrestrial atmosphere is the presence of 21 % O2, However, during most of the past 4 billion years, life and the surface environments on Earth were profoundly different than they are today. It is therefore a major goal of the astrobiology community to ascertain how the O2 content of the atmosphere has varied with time. and to understand the causes of these variations. The NAI and NASA Exobiology program have played critical roles in developing our current understanding of the ancient Earth's atmosphere, supporting diverse observational, analytical, and computational research in geoscience, life science, and related fields. In the present incarnation of the NAI, ongoing work is investigating (i) variations in atmospheric O2 in the Archean to the Cambrian, (ii) characterization of the redox state of the oceans shortly before, during and after the Great Oxidation Event (GOE), and (iii) unraveling the complex connections between environmental oxygenation, global climate, and the evolution of life

Uranium isotope cycling on the highly productive Peruvian margin

Uranium isotopes (δ238U values) in ancient sedimentary rocks (shales, carbonate rocks) are widely used as a tool to reconstruct paleo-redox conditions, but the behaviour of U isotopes under modern non-sulfidic anoxic vs. oxic conditions remains poorly constrained. We present U concentration and isotope data for modern sediments from the Peruvian margin, a highly productive open ocean environment with a range of redox conditions. To investigate U in different host fractions of the sediment (reactive, silicate, and HNO3-soluble fraction), we conducted a series of sequential extractions. Detrital-corrected authigenic U isotope compositions (δ238Uauth) in sediments deposited beneath an oxic water column show little deviation from the dissolved seawater U source, while anoxically deposited sediments have δ238Uauth values that are up to 0.4‰ heavier compared to seawater δ238U. Under anoxic, non-euxinic conditions, the U isotope offset between sediment and seawater is larger compared with oxic, but significantly smaller when compared with euxinic conditions from the literature. The results from sequential extractions show that the reactive sediment fraction records more pronounced differences in δ238Ureactive than δ238Uauth values depending on the oxidation state of the overlying water column. Furthermore, we found a strong correlation between total organic carbon (TOC) and both U concentrations (Uauth) and δ238Uauth values (R2 = 0.70 and 0.94, respectively) at the persistently anoxic site that we examined. These correlations can be caused by several processes including U isotope fractionation during microbially-mediated U reduction at the sediment-water interface (diffusive U input), during sorption onto and/or incorporation into organic matter in the water column (particulate U input) and diagenetic redistribution of U, or a combination of these processes. Our data show that several factors can influence δ238U values including oxidation state of U, the presence or absence of hydrogen sulfide and organic matter. These findings add new constraints to the degree of U isotope fractionation associated with U incorporation into sediments in different low-oxygen environments, thus aiding in interpretation of ancient paleo-redox conditions from U isotope data