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Dual replenisher system reduces chemical losses and maintains optimum solution concentration during long nonprocessing cycles of photo processing machines. Using a single 3-position switch and solenoid control valves, the system provides instantaneous flow control to each processing tank.
Not long after the discovery of the Antarctic ozone hole, it was established that halogen compounds, supplied to the atmosphere mainly by anthropogenic activities, are the primary driver of polar ozone loss. We will briefly review the chemical mechanisms that cause polar ozone loss and the early evidence showing the key role played by anthropogenic halogens. Recently, stratospheric halogen loading has leveled off, due to adherence to the Montreal Protocol and its amendments that has essentially banned CFCs (chlorofluorocarbons) and other halocarbons. We will describe recent reports of the first stage of recovery of the Antarctic ozone hole (e.g., a statistically significant slowing of the downward trend), associated with the leveling off of stratospheric halogens. Despite this degree of understanding, we will discuss the tendency of photochemical models to underestimate the observed rate of polar ozone loss and a hypothesis that has recently been put forth that might resolve this discrepancy. Finally, we will briefly discuss chemical loss of Arctic ozone, which
Analysis of data obtained by the backscatter ultraviolet (BUV) experiment on the Atmosphere Explorer E satellite has provided equatorial ozone mixing ratio profiles for equinox and solstice conditions. The combination of these results with a pure oxygen chemical model yields the rate of odd oxygen loss due to the sum of the odd hydrogen, nitrogen, and chlorine cycles. Use of recent mid-latitude stratospheric measurements of HO(x), NO(x), and ClO(x) with the BUV data provides an independent calculation of the catalytic loss. Below 45 km the agreement between the two sets of loss rates is satisfactory. At higher altitudes the odd hydrogen cycle provides far more O(x) loss than can be tolerated by the BUV measurements if the photodissociation of O2 is the only source and has the currently accepted magnitude. The results suggest either a tropical HO(x) concentration smaller than is now believed or the presence of a very large source of odd oxygen in the upper stratosphere and lower mesosphere.
In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.
In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.
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The Microwave Limb Sounder (MLS) observed ozone (O3) loss in the Arctic vortex beginning in January 1997 at 585 K (approximately 25 hPa) and in February 1997 at 465 K (approximately 50 hPa). Minimum vortex-averaged O3 mixing ratios observed in 1997 were higher than those in 1996, which were the lowest ever recorded by MLS. The vertical extent of O3 loss and maximum local O3 decreases were larger, but the decrease filled the vortex less completely, in 1997 than in 1996. Unusually low high-latitude column O3 above 100 hPa in April 1997 resulted mainly from dynamical effects of the unusually persistent lower stratospheric vortex and winter-like temperature patterns. Column O3 above 100 hPa averaged in comparable regions of the vortex showed a stronger decreasing trend in 1996-97 than in 1995-96, consistent with the larger vertical extent and maximum local values of lower stratospheric O3 loss. Chemical O3 loss resulted in an approximately 10% observed decrease in column O3 between late January and early April 1997.
The nonlinear chemical processes involved in ozone production (P(O3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O3) on volatile organic compounds (VOCs) or nitrogen oxides (NOx). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO2) has been widely used for studying O3 sensitivity. Previous studies found that the errors in retrievals and the incoherent relationship between the column and the near-surface concentrations are a barrier in applying the ratio in a robust way. In addition to these obstacles, we provide calculational-observational evidence, using an ensemble of 0-D photochemical box models constrained by DC-8 aircraft measurements on an ozone event during the Korea-United States Air Quality (KORUS-AQ) campaign over Seoul, to demonstrate the chemical feedback of NO2 on the formation of HCHO is a controlling factor for the transition line between NOx-sensitive and NOx-saturated regimes. A fixed value (~2.7) of the ratio of the chemical loss of NOx (LNOx) to the chemical loss of HO2+RO2 (LROx) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/NO2 less than 1 can be safely classified as NOx-saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO2 chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO2 ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNOx/LROx~2.7 that accounts for the HCHO-NO2 chemical relationship leading to HCHO = 3.7 × (NO2 – 1.14 × 1016 molec.cm-2). Although the revised formula is locally calibrated (i.e., requires for readjustment for other regions), its mathematical format removes the need for having a wide range of thresholds used in HCHO/NO2 ratios that is a result of the chemical feedback. Therefore, to be able to properly take the chemical feedback into consideration, the use of HCHO = a × (NO2 – b) formula should be preferred to the ratio in future works. We then use the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument to study O3 sensitivity in Seoul. The unprecedented spatial (250 × 250 m2) and temporal (~every 2 h) resolutions of HCHO and NO2 observations form the sensor enhance our understanding of P(O3) in Seoul; rather than providing a crude label for the entire city, more in-depth variabilities in chemical regimes are observed that should be able to inform mitigation strategies correspondingly.
Stratospheric and total columns of Arctic O3 (63-90 N) in late March 2011 averaged 320 and 349 DU, respectively. These values are 74 DU lower than averages for the previous 6 years. We use Aura MLS O3 observations to quantify the roles of chemistry and transport and find there are two major reasons for low O3 in March 2011: heterogeneous chemical loss and a late final warming that delayed the resupply of O3 until April. Daily vortex-averaged partial columns in the lowermost stratosphere (p greater than 133 hPa) and middle stratosphere (p less than 29 hPa) are unaffected by local heterogeneous chemistry and show a near total lack of transport into the vortex between late January and late March, contributing to the observed low column. The lower stratospheric (LS) column (133-29 hPa) is affected by both heterogeneous chemistry and transport. Low interannual variability of Aura MLS 0 3 columns and temperature inside the Arctic vortex (2004-2011) shows that the transport contribution to vortex O3 in fall and early winter is nearly the same each year. The descent of MLS N2O vortex profiles in 2011 provides an estimate of O3 transported into the LS column during late winter. By quantifying the role of transport we determine that PSC-driven chemical loss causes 80 (plus or minus 10) DU of vortex-averaged O3 loss by late March 2011. Without heterogeneous chemical loss, March 2011 vortex O3 would have been ~40 DU lower than normal due to the late final warming and resupply of O3 which did not occur until April.
The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2 ) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LRO x ) to the chemical loss of NO x (LNO x ). Subsequently, we challenge the predictive power of HCHO/NO 2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LRO x /LNO x . FNRs show a strongly linear (R 2 =0.94) relationship with LRO x /LNO x , but only on the logarithmic scale. Following the baseline (i.e., ln(LRO x /LNO x ) = −1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NO x -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the RO x –HO x cycle. We calculate high ozone production rates (PO 3 ) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NO x -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2 ). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm −2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric.
Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O 2 per gram of Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ after resting at upper capacity cut-offs of 135, 200 and 265 mAh g −1 for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li + . In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Furthermore, our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.
We use 25 new measurements of in situ produced cosmogenic 26 Al and 10 Be in river sand, paired with estimates of dissolved load flux in river water, to characterize the processes and pace of landscape change in central Cuba. Long-term erosion rates inferred from 10 Be concentrations in quartz extracted from central Cuban river sand range from 3.4–189 Mg km –2 yr –1 (mean 59, median 45). Dissolved loads (10–176 Mg km –2 yr –1 ; mean 92, median 97), calculated from stream solute concentrations and modeled runoff, exceed measured cosmogenic- 10 Be-derived erosion rates in 18 of 23 basins. This disparity mandates that in this environment landscape-scale mass loss is not fully represented by the cosmogenic nuclide measurements. The 26 Al / 10 Be ratios are lower than expected for steadystate exposure or erosion in 16 of 24 samples. Depressed 26 Al/ 10 Be ratios occur in many of the basins that have the greatest disparity between dissolved loads (high) and erosion rates inferred from cosmogenic nuclide concentrations (low). Depressed 26 Al/ 10 Be ratios are consistent with the presence of a deep, mixed, regolith layer providing extended storage times on slopes and/or burial and extended storage during fluvial transport. River water chemical analyses indicate that many basins with lower 26 Al/ 10 Be ratios and high 10 Be concentrations are underlain at least in part by evaporitic rocks that rapidly dissolve. Our data show that when assessing mass loss in humid tropical landscapes, accounting for the contribution of rock dissolution at depth is particularly important. In such warm, wet climates, mineral dissolution can occur many meters below the surface, beyond the penetration depth of most cosmic rays and thus the production of most cosmogenic nuclides. Our data suggest the importance of estimating solute fluxes and measuring paired cosmogenic nuclides to better understand the processes and rates of mass transfer at a basin scale.
Changes in lower stratospheric ozone caused by dynamical transport can be difficult to characterize and thus are sometimes difficult to distinguish from chemical losses. Correlations between ozone changes and various dynamical proxies (e.g., the eddy heat flux) from year to year can be of interest, but they do little in themselves to explain the ozone transport mechanisms behind such correlations. In this study, we use products from the Modern-Era Retrospective analysis for Research and Applications Version 2 (MERRA-2) to calculate the ozone mass flux, integrating it in space and time over the upper tropospheric/lower stratospheric Southern polar cap during periods when little chemical loss is expected. The ozone mass flux is expressed in terms of components of the residual circulation of the Transformed Eulerian Mean (TEM, i.e., 𝑣𝑣̅ ∗and 𝑤𝑤(∗) as well as eddy mixing terms. We relate these terms to the local ozone mass tendency ("#! "$ ), similarly integrated, and we find that the interannual variability of the ozone changes are strongly related to the residual meridional circulation and the meridional eddy mixing terms. These directly calculated dynamical transport terms provide clearer ozone proxies. Removing these advective terms from a long-term ozone time series can more effectively reveal ozone variations and long-term trends, specifically those caused by photochemical production and losses (e.g., human-produced ozone depletion).
A chemical transport model is used to investigate the processes that control the depth and duration of the ozone 'hole' in the lower stratosphere through comparisons of model output with measurements from the Total Ozone Mapping Spectrometer (TOMS) and from the Microwave Limb Sounder (MLS) and Halogen Occultation Experiment (HALOE), both on the Upper Atmosphere Research Satellite (UARS). This study extends previous model comparisons with observations into October and November and examine levels in (greater than 31 hPa) and above (less than 31 hPa) the chemical loss region. Averages of column ozone in the model decrease through mid-October below 31 hPa but begin to increase in mid-September above 31 hPa. An investigation of model-tracer data comparisons and other meteorological parameters indicate that the model presents a consistent picture of top-down recovery and tracer transport. An O03budget study at 500 K (below 31 hPa) and 840 K (above 31 hPa) is carried out to investigate the processes that control the timing of the transition of ozone from a chemical to dynamically driven regime. The model ozone decrease at 500 K is due to chemical loss in August and September but is due to upward motion in October. The ozone increase at 840 K is primarily due to photochemical production, with a smaller contribution from transport. These results show that chemistry and dynamics can play different roles in polar vortex ozone recovery at different levels.
During the winter of 1999-2000, the AROTEL instrument was deployed on the NASA DC-8 at Kiruna, Sweden for the SAGE III Ozone Loss Validation Experiment (SOLVE). Measurements of ozone, temperature and aerosols were made on 18 local science flights from December to March. Extremely low temperatures were observed throughout most of the Arctic vortex and polar stratospheric clouds were observed throughout the Arctic area during January. Significant ozone loss was measured after the sun began to rise on the vortex area in February. Ozone mixing ratios as low as 800 ppbv were observed during flights in March.
A faithful representation of polar stratospheric chemistry in models and its connection with dynamical variability is essential for our understanding of the evolution of the ozone layer in a changing climate and during the projected continuing decline of ozone depleting substances in the atmosphere. We use a new configuration of the Goddard Earth Observing System Data Assimilation System with a stratospheric chemistry model to study ozone depletion in the Arctic polar stratosphere during the exceptionally cold (in the stratosphere) winters 2015/2016 and 2010/2011.
Analyses of column ozone above 100 hPa (Col100) derived from Upper Atmosphere Research Satellite Microwave Limb Sounder (MLS) data in February/March 1992-1998 show that about half of the interannual variability in Col100 in the Arctic polar vortex in late winter results from interannual variability in chemical loss. A majority of the remainder results from interannual variability in day-to-day dynamical motions including adiabatic warming/cooling and poleward advection of underlying upper tropospheric subtropical air on short timescales, rather than from variations in descent rates and large-scale transport over the winters. The morphology of Col100 from MLS remains very similar to that in the dynamical models even in the years with most chemical ozone loss. The amount and character of day-to-day variability in dynamical models closely follows that in MLS Col100. Although the morphology of and day-to-day variability in Arctic column ozone are controlled by dynamical processes, chemical ozone loss was a major factor in producing both the low values of and the large interannual variability in Arctic column ozone observed during the 1990s.