The stability and calibration of water vapor isotope ratio measurements during long-term deployments

With the recent advent of commercial laser absorption spectrometers, field studies measuring stable isotope ratios of hydrogen and oxygen in water vapor have proliferated. These pioneering analyses have provided invaluable feedback about best strategies for optimizing instrumental accuracy, yet questions still remain about instrument performance and calibration approaches for multi-year field deployments. With clear scientific potential for using these instruments to carry out monitoring of the hydrological cycle, this study examines the long-term stability of the isotopic biases associated with three cavity-enhanced laser absorption spectrometers - calibrated with different systems and approaches - at two remote field sites: Mauna Loa Observatory, Hawaii, USA, and Greenland Environmental Observatory, Summit, Greenland. The analysis pays particular attention to the stability of measurement dependencies on water vapor concentration and also evaluates whether these so-called concentration dependences are sensitive to statistical curve-fitting choices or measurement hysteresis. The results suggest evidence of monthly-to-seasonal concentration-dependence variability - which likely stems from low signal-to-noise at the humidity-range extremes - but no long-term directional drift. At Mauna Loa, where the isotopic analyzer is calibrated by injection of liquid water standards into a vaporizer, the largest source of inaccuracy in characterizing the concentration dependence stems from an insufficient density of calibration points at low water vapor volume mixing ratios. In comparison, at Summit, the largest source of inaccuracy is measurement hysteresis associated with interactions between the reference vapor, generated by a custom dew point generator, and the sample tubing. Nevertheless, prediction errors associated with correcting the concentration dependence are small compared to total measurement uncertainty. At both sites, changes in measurement repeatability that are not predicted by long-term linear drift estimates are a larger source of error, highlighting the importance of measuring isotopic standards with minimal or well characterized drift at regular intervals. Challenges in monitoring isotopic drift are discussed in light of the different calibration systems evaluated

The stability and calibration of water vapor isotope ratio measurements during long-term deployments

With the recent advent of commercial laser absorption spectrometers, field studies measuring stable isotope ratios of hydrogen and oxygen in water vapor have proliferated. These pioneering analyses have provided invaluable feedback about best strategies for optimizing instrumental accuracy, yet questions still remain about instrument performance and calibration approaches for multi-year field deployments. With clear scientific potential for using these instruments to carry out long-term monitoring of the hydrological cycle, this study examines the long-term stability of the isotopic biases associated with three cavity-enhanced laser absorption spectrometers – calibrated with different systems and approaches – at two remote field sites: Mauna Loa Observatory, Hawaii, USA, and Greenland Environmental Observatory, Summit, Greenland. The analysis pays particular attention to the stability of measurement dependencies on water vapor concentration and also evaluates whether these so-called concentration-dependences are sensitive to statistical curve-fitting choices or measurement hysteresis. The results suggest evidence of monthly-to-seasonal concentration-dependence variability – which likely stems from low signal-to-noise at the humidity-range extremes – but no long-term directional drift. At Mauna Loa, where the isotopic analyzer is calibrated by injection of liquid water standards into a vaporizer, the largest source of inaccuracy in characterizing the concentration-dependence stems from an insufficient density of calibration points at low humidity. In comparison, at Greenland, the largest source of inaccuracy is measurement hysteresis associated with interactions between the reference vapor, generated by a custom dew point generator (DPG), and the sample tubing. Nevertheless, prediction errors associated with correcting the concentration-dependence are small compared to total measurement uncertainty. At both sites, a dominant source of uncertainty is instrumental precision at low humidity, which cannot be reduced by improving calibration strategies. Challenges in monitoring long-term isotopic drift are also discussed in light of the different calibration systems evaluated.The final revised paper is available at: http://hdl.handle.net/1957/5787

Ecosystem fluxes of carbonyl sulfide in an old-growth forest: temporal dynamics and responses to diffuse radiation and heat waves

Carbonyl sulfide (OCS) has recently emerged as a tracer for terrestrial carbon uptake. While physiological studies relating OCS fluxes to leaf stomatal dynamics have been established at leaf and branch scales and incorporated into global carbon cycle models, the quantity of data from ecosystem-scale field studies remains limited. In this study, we employ established theoretical relationships to infer ecosystem-scale plant OCS uptake from mixing ratio measurements. OCS fluxes showed a pronounced diurnal cycle, with maximum uptake at midday. OCS uptake was found to scale with independent measurements of CO2 fluxes over a 60&thinsp;m tall old-growth forest in the Pacific Northwest of the US (45∘49′13.76′′&thinsp;N, 121∘57′06.88′′&thinsp;W) at daily and monthly timescales under mid–high light conditions across the growing season in 2015. OCS fluxes were strongly influenced by the fraction of downwelling diffuse light. Finally, we examine the effect of sequential heat waves on fluxes of OCS, CO2, and H2O. Our results bolster previous evidence that ecosystem OCS uptake is strongly related to stomatal dynamics, and measuring this gas improves constraints on estimating photosynthetic rates at the ecosystem scale.</p

Evidence for solar cycles in a late Holocene speleothem record from Dongge Cave, China

The association between solar activity and Asian monsoon (AM) remains unclear. Here we evaluate the possible connection between them based on a precisely-dated, high-resolution speleothem oxygen isotope record from Dongge Cave, southwest China during the past 4.2 thousand years (ka). Without being adjusted chronologically to the solar signal, our record shows a distinct peak-to-peak correlation with cosmogenic nuclide 14C, total solar irradiance (TSI) and sunspot number (SN) at multi-decadal to centennial timescales. Further cross-wavelet analyses between our calcite δ18O and atmospheric 14C show statistically strong coherence at three typical periodicities of ~80, 200 and 340 years, suggesting important roles of solar activities in modulating AM changes at those timescales. Our result has further indicated a better correlation between our calcite δ18O record and atmospheric 14C than between our record and TSI. This better correlation may imply that the Sun–monsoon connection is dominated most likely by cosmic rays and oceanic circulation (both associated to atmospheric 14C), instead of the direct solar heating (TSI)

Constraining surface carbon fluxes using in situ measurements of carbonyl sulfide and carbon dioxide

Understanding the processes that control the terrestrial exchange of carbon is critical for assessing atmospheric CO₂ budgets. Carbonyl sulfide (COS) is taken up by vegetation during photosynthesis following a pathway that mirrors CO₂ but has a small or nonexistent emission component, providing a possible tracer for gross primary production. Field measurements of COS and CO₂ mixing ratios were made in forest, senescent grassland, and riparian ecosystems using a laser absorption spectrometer installed in a mobile trailer. Measurements of leaf fluxes with a branch-bag gas-exchange system were made across species from 10 genera of trees, and soil fluxes were measured with a flow-through chamber. These data show (1) the existence of a narrow normalized daytime uptake ratio of COS to CO₂ across vascular plant species of 1.7, providing critical information for the application of COS to estimate photosynthetic CO₂ fluxes and (2) a temperature-dependent normalized uptake ratio of COS to CO₂ from soils. Significant nighttime uptake of COS was observed in broad-leafed species and revealed active stomatal opening prior to sunrise. Continuous high-resolution joint measurements of COS and CO₂ concentrations in the boundary layer are used here alongside the flux measurements to partition the influence that leaf and soil fluxes and entrainment of air from above have on the surface carbon budget. The results provide a number of critical constraints on the processes that control surface COS exchange, which can be used to diagnose the robustness of global models that are beginning to use COS to constrain terrestrial carbon exchange.Keywords: surface fluxes, carbonyl sulfide, laser absorption spectrometry, carbon budget, instrument developmen

Supercooled liquid fogs over the central Greenland Ice Sheet

Radiation fogs at Summit Station, Greenland (72.58∘&thinsp;N, 38.48∘&thinsp;W; 3210&thinsp;m&thinsp;a.s.l.), are frequently reported by observers. The fogs are often accompanied by fogbows, indicating the particles are composed of liquid; and because of the low temperatures at Summit, this liquid is supercooled. Here we analyze the formation of these fogs as well as their physical and radiative properties. In situ observations of particle size and droplet number concentration were made using scattering spectrometers near 2 and 10&thinsp;m height from 2012 to 2014. These data are complemented by colocated observations of meteorology, turbulent and radiative fluxes, and remote sensing. We find that liquid fogs occur in all seasons with the highest frequency in September and a minimum in April. Due to the characteristics of the boundary-layer meteorology, the fogs are elevated, forming between 2 and 10&thinsp;m, and the particles then fall toward the surface. The diameter of mature particles is typically 20&ndash;25&thinsp;&micro;m in summer. Number concentrations are higher at warmer temperatures and, thus, higher in summer compared to winter. The fogs form at temperatures as warm as &minus;5&thinsp;∘C, while the coldest form at temperatures approaching &minus;40&thinsp;∘C. Facilitated by the elevated condensation, in winter two-thirds of fogs occurred within a relatively warm layer above the surface when the near-surface air was below &minus;40&thinsp;∘C, as cold as &minus;57&thinsp;∘C, which is too cold to support liquid water. This implies that fog particles settling through this layer of cold air freeze in the air column before contacting the surface, thereby accumulating at the surface as ice without riming. Liquid fogs observed under otherwise clear skies annually imparted 1.5&thinsp;W&thinsp;m&minus;2 of cloud radiative forcing (CRF). While this is a small contribution to the surface radiation climatology, individual events are influential. The mean CRF during liquid fog events was 26&thinsp;W&thinsp;m&minus;2, and was sometimes much higher. An extreme case study was observed to radiatively force 5&thinsp;∘C of surface warming during the coldest part of the day, effectively damping the diurnal cycle. At lower elevations of the ice sheet where melting is more common, such damping could signal a role for fogs in preconditioning the surface for melting later in the day. </div

The nocturnal water cycle in an open-canopy forest

The movement of moisture into, out-of, and within forest ecosystems is modulated by feedbacks that stem from processes which couple plants, soil, and the atmosphere. While an understanding of these processes has been gleaned from Eddy Covariance techniques, the reliability of the method suffers at night because of weak turbulence. During the summer of 2011, continuous profiles of the isotopic composition (i.e., δ¹⁸O and δD) of water vapor and periodic measurements of soil, leaf, and precipitation pools were measured in an open-canopy ponderosa pine forest in central Colorado to study within-canopy nocturnal water cycling. The isotopic composition of the nocturnal water vapor varies significantly based on the relative contributions of the three major hydrological processes acting on the forest: dewfall, exchange of moisture between leaf waters and canopy vapor, and periodic mixing between the canopy and background air. Dewfall proved to be surprisingly common (~30% of the nights) and detectable on both the surface and within the canopy through the isotopic measurements. While surface dew could be observed using leaf wetness and soil moisture sensors, dew in the foliage was only measurable through isotopic analysis of the vapor and often occurred even when no dew accumulated on the surface. Nocturnal moisture cycling plays a critical role in water availability in forest ecosystems through foliar absorption and transpiration, and assessing these dynamics, as done here, is necessary for fully characterizing the hydrological controls on terrestrial productivity.Keywords: dewfall, nocturnal boundary layer, water isotopes, forest hydrolog

Morphine paradoxically prolongs neuropathic pain in rats by amplifying spinal NLRP3 inflammasome activation

Pain after disease/damage of the nervous system is predominantly treated with opioids, but without exploration of the long-term consequences. We demonstrate that a short course of morphine after nerve injury doubles the duration of neuropathic pain. Using genetic and pharmacological interventions, and innovative Designer Receptor Exclusively Activated by Designer Drugs disruption of microglia reactivity, we demonstrate that opioid-prolonged neuropathic pain arises from spinal microglia and NOD-like receptor protein 3 inflammasome formation/activation. Inhibiting these processes permanently resets amplified pain to basal levels, an effect not previously reported. These data support the “two-hit hypothesis” of amplification of microglial activation—nerve injury being the first “hit,” morphine the second. The implications of such potent microglial “priming” has fundamental clinical implications for pain and may extend to many chronic neurological disorders

End of Green Sahara amplified mid- to late Holocene megadroughts in mainland Southeast Asia

Between 5 and 4 thousand years ago, crippling megadroughts led to the disruption of ancient civilizations across parts of Africa and Asia, yet the extent of these climate extremes in mainland Southeast Asia (MSEA) has never been defined. This is despite archeological evidence showing a shift in human settlement patterns across the region during this period. We report evidence from stalagmite climate records indicating a major decrease of monsoon rainfall in MSEA during the mid- to late Holocene, coincident with African monsoon failure during the end of the Green Sahara. Through a set of modeling experiments, we show that reduced vegetation and increased dust loads during the Green Sahara termination shifted the Walker circulation eastward and cooled the Indian Ocean, causing a reduction in monsoon rainfall in MSEA. Our results indicate that vegetation-dust climate feedbacks from Sahara drying may have been the catalyst for societal shifts in MSEA via ocean-atmospheric teleconnections