The way forward for Montreal Protocol science

The Montreal Protocol has controlled the production and consumption of ozone-depleting substances (ODSs) since its signing in 1987. The levels of most of these ODSs are now declining in the atmosphere, and there are now initial signs that ozone levels are increasing in the stratosphere. Scientific challenges remain for the Montreal Protocol. The science community projected large ozone losses if ODSs continued to increase, and that ozone levels would increase if ODSs were controlled and their levels declined. Scientists remain accountable for these projections, while they continue to refine their scientific basis. The science community remains vigilant for emerging threats to the ozone layer and seeks scientific evidence that demonstrates compliance with Montreal Protocol. As ODSs decrease, the largest impact on stratospheric ozone by the end of the 21st century will be increases in greenhouse gases. The associated climate forcings, and the human responses to these forcings, represent major uncertainties for the future of the stratospheric ozone layer.     

The global search and commercialization of alternatives and substitutes for ozone-depleting substances

The Montreal Protocol has halted 99% of global production of chemical substances that deplete stratospheric ozone, which protects life on earth from the harmful effects of ultraviolet (UVB) radiation. UVB causes skin cancer and cataracts, suppresses the human immune system, destroys plastics, and damages agricultural crops and natural ecosystems. Because ozone-depleting substances (ODSs) are powerful greenhouse gases, the Montreal Protocol also protects climate. From the authors’ perspectives in multiple roles as environmental entrepreneurs, practitioners, and authorities, this paper explains how individuals, companies, and military organizations researched, developed, commercialized and implemented alternatives to ODSs that are also safer for climate. With the benefit of hindsight, the authors reflect on what was neglected or done badly under the Montreal Protocol and present lessons learned on how Montreal Protocol institutions can be renewed and revitalized to phase down hydrofluorocarbons (HFCs).     

The role and performance of ground-based networks in tracking the evolution of the ozone layer

In the 1980s, ground-based monitoring of the ozone layer played a key role in the discovery of the Antarctic Ozone Hole as well as in the first documentation of significant winter and spring long-term downward trends in the populated mid-latitude regions. The article summarizes the close-to-hundred-year-long history of ground-based measurements of stratospheric ozone, and more recent observations of constituents that influence its equilibrium. Ozone observations began long before the recognition of the impact of increasing emissions of manmade ozone-depleting substances on ozone and therefore on UV levels, human health, ecosystems and the Earth climate. The historical ozone observations prior to 1980s are used as a reference for the assessments of the state of the ozone layer linked to the enforcement of the Montreal Protocol. In this paper, we describe the worldwide monitoring networks and their ozone observations used to determine long-term trends with an accuracy of a few percent per decade. Since 1989, the ground-based monitoring activities have provided support for the amendments of the Montreal Protocol (MP). They include monitoring of (a) the ozone total column and the vertical distribution at global scale, (b) the ozone-depleting substances (ODS) related to the MP such as chlorofluorocarbons (CFCs), and their decomposition products in the stratosphere, and (c) the atmospheric species playing a role in ozone depletion, e.g., nitrogen oxides, water vapor, aerosols, polar stratospheric clouds. We highlight important accomplishments in the atmospheric monitoring performed by the Global Atmosphere Watch program (GAW) run under the auspices of the World Meteorological Organization (WMO) and by the Network for the Detection of Atmospheric Composition Change (NDACC). We also address the complementary roles of ground-based networks and satellite instruments. High-quality ground-based measurements have been used to evaluate ozone variabilities and long-term trends, assess chemistry climate models, and check the long-term stability of satellite data, including more recently the merged satellite time-series developed for the detection of ozone recovery at global scale, which might be further modified by climate change.     

Future ozone in a changing climate

The stratospheric ozone layer is expected to recover as a result of the regulations of the Montreal Protocol on chlorine and bromine containing ozone-depleting substances (ODSs). Model simulations project a return of global annually averaged total column ozone to 1980 levels before the middle of the 21^st century, well before the ODSs will return to 1980 levels. This earlier ozone return date is due to the effects of rising greenhouse gas (GHG) concentrations. GHGs influence ozone directly by chemical reactions, but also indirectly by changing stratospheric temperature and the Brewer–Dobson circulation. Based on projections of chemistry–climate models, this article summarizes the effects of GHGs on stratospheric and total column ozone in the mid-latitude upper stratosphere, Arctic and Antarctic spring, and the tropics. The sensitivity of future ozone change to the GHG scenario is discussed, as well as the specific role of a future increase in nitrous oxide and methane.     

Montreal Protocol at 30: The governance structure,the evolution,and the Kigali Amendment

Scientific discoveries, national regulations, and international agreements impact our lives. If we bring all three together in a solid but flexible governance structure, then we are able to address those impacts and share more evenly their consequences across different nations. This is what the Montreal Protocol has done in its 30 years of life and will continue to do thanks to the recent Kigali Amendment. There are many lessons for diplomacy to be drawn from the recent negotiations, including the critical role of science. The most important lesson in reaching consensus is the injection of optimism, pride, ownership of the process, and building trust among all nations. The solid yet flexible foundation of the Montreal Protocol provided a firm grounding for the Kigali negotiations to experiment with the different negotiating techniques in a forum where countries, industry, non-governmental organizations, and scientists are brought together by the United Nations.     

Spatial observation of the ozone layer

This article provides an overview of the various satellite instruments, which have been used to observe stratospheric ozone and other chemical compounds playing a key role in stratospheric chemistry. It describes the various instruments that have been launched since the late 1970s for the measurement of total ozone column and ozone vertical profile, as well as the major satellite missions designed for the study of stratospheric chemistry. Since the discovery of the ozone hole in the early 1980s, spatial ozone measurements have been widely used to evaluate and quantify the spatial extension of polar ozone depletion and global ozone decreasing trends as a function of latitude and height. Validation and evaluation of satellite ozone data have been the subject of intense scientific activity, which was reported in the various ozone assessments of the state of the ozone layer published after the signature of the Montreal protocol. Major results, based on satellite observations for the study of ozone depletion at the global scale and chemical polar ozone loss, are provided. The use of satellite observations for the validation of chemistry climate models that simulate the recovery of the ozone layer and in data assimilation is also described.     

Geomagnetic anomalies and regional geology in India along 18° N parallel

The mobile geomagnetic measurements made during 1970–73 by NGRI across the Indian Peninsula between Alibag and Kalingapatnam have been examined. It is noticed that the meanZ values after normal correction and the long periodZr/Hr ratio reveal different levels on the three different geological provincesviz., the Deccan traps, peninsular granites and the easternghat metamorphics.     

Emission quantification of refrigerant CFCs,HCFCs and HFCs in megacity Lahore (Pakistan) and contributed ODPs and GWPs

An integrated assessment of emissions of some important refrigerant ozone depleting substances (ODSs) (CFC-11, CFC-12, HCFC-141b and HFC-134a) and their contributed ozone depletion potentials (ODPs) and global warming potentials (GWPs) have been made in the megacity Lahore (Pakistan) for the period from 2005 to 2013. During the production of 6.488 million refrigerator units, the cumulative estimated emissions of CFC-11, CFC-12, HCFC-141b and HFC-134a were 129.7, 6.8, 1257 and 104 mega grams (1 Mg = 10⁶ grams). The estimated GWP (CO₂-eq) and ODP (CFC 11-eq) associated with production phase emissions of these four gases were 616.07, 73.52, 910.96, and 87.36 kilotonnes, and 129.7, 6.8, 139.4, and 0 tonnes, respectively. ODP of HFC-134a is considered to be zero. In addition, the repair and maintenance of 81.2 thousand units resulted in 10.8 Mg emissions of CFC-12 with 10.8 tonnes ODP(CFC 11-eq) and 117,802 tonnes GWP (CO₂-eq) that were higher than the HFC-134a emissions recorded at 4.3 Mg causing 4563 tonnes GWP(CO₂-eq). A decrease in ODP (CFC 11-eq) and GWP (CO₂-eq) at the rate of ?8.3% and ?8.2% per year is observed to be contributed by all the selected ODSs during the study period.     

Natural background levels for some ions in groundwater of the Campania region (southern Italy)

The aim of the study was the determination of the natural background levels (NBLs) for the ions Na⁺, Cl^?, SO₄ ^2?, As³⁺, F^?, Fe²⁺, and Mn²⁺, in some groundwater bodies of the Campania region (southern Italy). The ??Protocol to evaluate the natural background concentrations?? proposed in 2009 by ISPRA (Italian Institute for Environmental Protection and Research) has been applied to the chemical data set of groundwater of the examined groundwater bodies. These analyses have also been examined following the guidelines of the BRIDGE project (Background cRiteria for the IDentification of Groundwater thrEshold). These approaches to evaluate the Threshold Values (TVs) and the NBLs, based on probability distribution functions, have been applied in many countries by various authors during the last 5?years. Changes applied to ISPRA Protocol in this study concern mainly the preselection criteria, in particular threshold values of specific ions, deriving from the aquifers geochemical features. The preselection criteria of the ISPRA Protocol have been merged with those of the BRIDGE Project in order to define a procedure suitable for the definition of the NBLs in the examined aquifers. The NBL of fluoride for the ??Phlegrean Fields?? and the ??eastern Plain of Naples?? groundwater bodies shows values deeply exceeding the reference value (REF) of 1,500???g/L, ranging between 3,600 and 15,000???g/L. The cause of this very high fluoride content is in the natural features of the aquifers constituted by volcanic and pyroclastic rocks. The volcanic origin of the aquifers is also the reason for the high arsenic content in ??Phlegrean Fields?? groundwater. Here the NBL calculated was about 47???g/L against the drinking water standard value of 10???g/L. The widespread high content of manganese and iron for the groundwater body of the ??eastern Plain of Naples?? is due to the reducing conditions related to the extensive marshlands present in the past. The very high NBL of all the examined ions for the groundwater body of ??Ischia Island?? depends on the existence of a geothermal system.     

The gypsum-anhydrite equilibrium by solubility measurements

Solubility measurements have been used to establish the gypsum-anhydrite equilibrium in the CaSO₄-H₂O system at atmospheric pressure. The saturation equilibrium has been approached both from undersaturated and supersaturated solutions. The invariant point temperature has been found to be 49.5 ± 2.5°C.     

Temperature variation in the mesosphere during solar eclipse

Rocket-borne observations of the extinction of solar hydrogen Lyman-alpha radiation made during the solar eclipses of 20 May 1966 at Karistos for normal and 44% visibility and of 7 March 1970 at East Quoddy for normal, 10% and 0.6% visibility have been used to study the variation of temperature in the mesosphere during these events. It is seen that near the mesopause the decrease of temperature at Karistos is by 20° K for 44% visibility and at East Quoddy by 100° K for 0.6% visibility. Possible causes of these temperature variationsvis-a-vis molecular oxygen and pressure variations have been briefly discussed.     

Celestite (SrSO4(s)) solubility in water,seawater and NaCl solution

Celestite solubility measurements have been conducted in pure water at temperatures from 10 to 90°C. Equilibrium was achieved with respect to a crystalline solid phase from both undersaturated and supersaturated solutions. The measurements show that the solubility undergoes a maximum near 20°C. LogK values for the solubility reaction are adequately described by the following expression over the temperature range 283.15 to 363.15 K: −logK= −35.3106+0.00422837T+318312/T²+14.99586 logT.The following thennodynamic values for the dissolution reaction of SrSO_4(s), at 25°C have been derived: ΔG_R⁰ = 37852 ± 30 Jmol⁻¹ΔH_R⁰ = −1668±920Jmol⁻¹ΔS_R⁰= −132.6±3.2JK^−1mol−1Celestite solubility measurements were also determined in NaCl solutions up to 5 m concentration and from 10 to 40°C. These data are in good agreement with the work of StrÜbel (1966), who reports solubility measurements to temperatures of 100°C.The application of the Pitzer relations and the solubility constants determined in this study to calculate celestite solubility in NaCl solutions yields excellent agreement between predicted values and experimental measurements over the entire range of temperature and NaCl concentration conditions. For the limited number of solubility measurements in seawater-type solutions and mixed-salt brines, the agreement using the Pitzer relations is within three percent of the measured solubility.     

Distribution and abundance of submerged aquatic vegetation in Chesapeake Bay: An historical perspective

An historical summary of the distribution and abundance of submerged aquatic vegetation (SAV) in the Chesapeake Bay is presented. Evidence suggests that SAV has generally been common throughout the bay over the last several hundred years with several fluctuations in abundance. The decline ofZostera marina (eelgrass) in the 1930’s and the rapid expansion ofMyriophyllum spicatum (watermilfoil) in the late 1950’s and early 1960’s were two significant events involving a single species. Since 1965, however, there has been a significant reduction of all species in most sections of the bay. Declines were first observed in the Patuxent, Potomac and sections of other rivers in the Maryland portion of the Bay between 1965 and 1970. Dramatic reductions were observed over the entire length of the bay from 1970 to 1975. Particularly severe losses were observed at the head of the bay around Susquehanna Flats as well as in numerous rivers along Maryland’s eastern and western shores. Changes in the lower, Virginia portion of the bay occurred primarily in the western tributaries. Greatest losses of vegetation occurred in the years following Tropical Storm Agnes in 1972. Since 1975 little regrowth has been observed in the Chesapeake Bay. Other areas along the Atlantic Coast of the U.S. during the same period have experienced no similar widespread decline. It thus appears that the factors affecting the recent changes in distribution and abundance of submerged vegetation in the bay are regional in nature. Causes for this decline may be related to changes in water quality, primarily increased eutrophication and turbidity.     

Anthropogenic versus natural control on trace element and Sr-Nd-Pb isotope stratigraphy in peat sediments of southeast Florida (USA), ∼1500 AD to present

Analysis of a well-dated peat core from Blue Cypress Marsh (BCM) provides a detailed record of natural and anthropogenic factors that controlled the geochemical cycles of a number of trace elements in Florida over the last five centuries. The trace elements were divided into “natural” and “anthropogenic” groups using concentration trends from the bottom to the top of the core. The “natural” group includes Li, Sc, Cr, Co, Ga, Ge, Zr, Nb, Cs, Ba, Hf, Y, Ta, Th, and REE (Rare Earth Elements). These elements show similar concentrations throughout the core, indicating that changes in human activities after European arrival in the “New World” did not affect their geochemical cycles. The “anthropogenic” group includes Pb, Cu, Zn, V, Sb, Sn, Bi, and Cd. Upcore enrichment of these elements indicates enhancement by anthropogenic activities. From the early 1500s to present, fluxes of the “anthropogenic” metals to the marsh increased significantly, with modern accumulation rates several-fold (e.g., V) to hundreds of times (e.g., Zn) greater than pre-colonial rates. The dominant input mechanism for trace elements from both groups to the marsh has been atmospheric deposition. Atmospheric input of a number of the elements, including the anthropogenic metals, was dominated by local sources during the last century. For several elements, long-distant transport may be important. For instance, REE and Nd isotopes provide evidence for long-range atmospheric transport dominated by Saharan dust.The greatest increase in flux of the “anthropogenic” metals occurred during the 20th century and was caused by changes in the chemical composition of atmospheric deposition entering the marsh. Increased atmospheric inputs were a consequence of several anthropogenic activities, including fossil fuel combustion (coal and oil), agricultural activities, and quarrying and mining operations. Pb and V exhibit similar trends, with peak accumulation rates in 1970. The principal anthropogenic source of V is oil combustion. The decline in V accumulation after 1970 in the BCM peat corresponds to the introduction of low-sulfur fuels and the change from heavy to distilled oils since the 1970s. After the 1920s, Pb distribution in the peat follows closely the history of alkyl lead consumption in the US, which peaked in the 1970s. Pb isotopes support this inference and furthermore, record changes in the ore sources used to produce leaded gasoline. Idaho ores dominated the peat Pb isotope record until the 1960s, followed by Pb from Mississippi Valley Type deposits from the 1960s to the 1980s. Enhanced fluxes of Cu, Zn, Cd, Sn, Sb, Bi, and to some extent Ni during the last century are likely also related to fossil fuel combustion. Local agricultural activities may also have influenced the geochemical cycles of Cu and Zn. The peat record shows enhanced U accumulation during the last century, possibly related to phosphate mining in western Florida. Sr isotopes in the peat core also reflect anthropogenic influence. The ⁸⁷Sr/⁸⁶Sr ratio decreases from natural background values in the basal part of the core to lower values in the upper part of the core. The Sr isotope shift is probably related to quarrying operations in Florida, and marks the first time an anthropogenic signal has been detected using the Sr isotope record in a peat core.     

Is global ozone recovering?

Thanks to the Montreal Protocol, the stratospheric concentrations of ozone-depleting chlorine and bromine have been declining since their peak in the late 1990s. Global ozone has responded: The substantial ozone decline observed since the 1960s ended in the late 1990s. Since then, ozone levels have remained low, but have not declined further. Now general ozone increases and a slow recovery of the ozone layer is expected. The clearest signs of increasing ozone, so far, are seen in the upper stratosphere and for total ozone columns above Antarctica in spring. These two regions had also seen the largest ozone depletions in the past. Total column ozone at most latitudes, however, does not show clear increases yet. This is not unexpected, because the removal of chlorine and bromine from the stratosphere is three to four times slower than their previous increase. Detecting significant increases in total column ozone, therefore, will require much more time than the detection of its previous decline. The search is complicated by variations in ozone that are not caused by declining chlorine or bromine, but are due, e.g., to transport changes in the global Brewer–Dobson circulation. Also, very accurate observations are necessary to detect the expected small increases. Nevertheless, observations and model simulations indicate that the stratosphere is on the path to ozone recovery. This recovery process will take many decades. As chlorine and bromine decline, other factors will become more important. These include climate change and its effects on stratospheric temperatures, changes in the Brewer–Dobson circulation (both due to increasing CO₂), increasing emissions of trace gases like N₂O, CH₄, possibly large future increases of short-lived substances (like CCl₂H₂) from both natural and anthropogenic sources, and changes in tropospheric ozone.     

The RANSAC Method for Generating Fracture Networks from Micro-seismic Event Data

Fracture network modeling is an essential part of the design, development and performance assessment of Enhanced Geothermal Systems. These systems are created from geothermal resources, usually located several kilometers below the surface of the Earth, by establishing a network of connected fractures through which fluid can flow. The depth of the reservoir makes it impossible to make direct measurements of fractures and data are collected from indirect measurements such as geophysical surveys. An important source of indirect data is the seismic event point cloud generated by the fracture stimulation process. Locations of these points are estimated from recorded micro-seismic signals generated by fracture initiation, propagation and slip. This point cloud can be expressed as a set of three-dimensional coordinates with attributes, for example Se _ijk ={(x,y,z);?a|x,y,z∈R,?a∈I}. We describe two methods for reconstructing realistic fracture trace lines and planes given the point cloud of seismic events data: Enhanced Brute-Force Search and RANSAC. The methods have been tested on a synthetic data set and on the Habanero data set of Geodynamics’ geothermal project in the Cooper Basin of South Australia. Our results show that the RANSAC method is an efficient and suitable method for the conditional simulation of fracture networks.     

An application of artificial intelligence for investigating the effect of COVID-19 lockdown on three-dimensional temperature variation in equatorial Africa

We present interesting application of artificial intelligence for investigating effect of the COVID-19 lockdown on 3-dimensional temperature variation across Nigeria (2°–15° E, 4°–14° N), in equatorial Africa. Artificial neural networks were trained to learn time-series temperature variation patterns using radio occultation measurements of atmospheric temperature from the Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC). Data used for training, validation and testing of the neural networks covered period prior to the lockdown. There was also an investigation into the viability of solar activity indicator (represented by the sunspot number) as an input for the process. The results indicated that including the sunspot number as an input for the training did not improve the network prediction accuracy. The trained network was then used to predict values for the lockdown period. Since the network was trained using pre-lockdown dataset, predictions from the network are regarded as expected temperatures, should there have been no lockdown. By comparing with the actual COSMIC measurements during the lockdown period, effects of the lockdown on atmospheric temperatures were deduced. In overall, the mean altitudinal temperatures rose by about 1.1 °C above expected values during the lockdown. An altitudinal breakdown, at 1 km resolution, reveals that the values were typically below 0.5 °C at most of the altitudes, but exceeded 1 °C at 28 and 29 km altitudes. The temperatures were also observed to drop below expected values at altitudes of 0–2 km, and 17–20 km.     

从第三极到北极： 气候与冰冻圈变化及其影响

第三极和北极地区对于区域和全球环境、 社会经济以及国家战略的重要性日益凸现。通过对第三极和北极气候与冰冻圈研究的现状、 趋势进行梳理总结, 为未来的系统研究提供借鉴。结果显示, 第三极和北极气候系统与冰冻圈正在发生显著变化并预计将持续下去。第三极和北极地区气温在以全球平均升温速度两倍的速率变暖, 且在20世纪70年代以来, 变化总体趋势高度一致; 降水变化总体呈增加趋势, 但变率和不确定性较大; 极端事件（尤其是极端降水）的频率增加; 积雪范围总体上呈现减少趋势, 雪水当量、 积雪天数的变化存在区域和周期性差异; 多年冻土温度升高, 活动层厚度增加, 亦呈现较大的区域差异。这些变化不仅对生态、 水文、 碳循环产生重要影响, 而且对基础设施、 社会经济以及人类健康产生不可忽视的影响, 包括重金属污染、 食品安全等。气候及冰冻圈快速变化会通过反照率反馈、 水汽反馈等机制被放大, 并通过一系列大气及海洋环流过程, 对周边乃至全球气候系统产生广泛影响。目前第三极和北极研究中面临的重要共同问题包括极度稀疏的地面观测资料、 模型物理机制和精细化描述不足以及缺少与周边地区乃至全球系统关联的量化研究和可靠证据。这些问题的解决都需要依赖地面监测网络的扩展以及对冰冻圈和气候系统物理过程理解的提升。从第三极到北极, 不仅是研究视角的扩大, 更是全面理解第三极和北极在地球系统中作用的必经之路。     

Geodetic networks along the Caribbean-South-American plate boundary

Three major fault zones form the Caribbean-South-American plate boundary; these are the Bocono, Moron, and Pilar fault zones. The first geodetic networks were explored and installed in 1972–1973. First measurements were realized in 1973 and remeasurements were made at several intervals up to date. In total 18 sites were studied and explored for local geodetic networks; of these, only five are completely operational, the others are still waiting for monumentation and operation. Nevertheless, for these latter, the main part of the installation, the exploration work and the feasibility studies in geology and topography have already been realized. In the operational networks, the field and point vectors show movements and deformations. Max. values: Yacambu 88 mm/2 years, Mucubaji 32 mm/5 years. The deformational parts of displacements show principally compression vectors from both sides towards the plate boundary.     

Instability of the kinematic state in the atmosphere of the hypergiant ρ Cas outside outburst

Multiple observations of the yellow hypergiant ρ Cas obtained in 2007–2011 in a wide wavelength range with spectroscopic resolving power R ≥ 60 000 have enabled studies of features of its optical spectrum in detail and brought to light previously unknown characteristics of the star’s extended atmosphere. The radial velocity measured from symmetric absorption lines of metals varies with an amplitude of about ±7 km/s around the systemic velocity V _sys = ?47 km/s, due to low-amplitude pulsations of the atmospheric layers near the photosphere. At some times, a velocity gradient was observed in deep atmospheric layers of the star. A slight velocity stratification in the stellar atmosphere was detected for the first time, manifest as a difference of 3–4 km/s in the velocities measured from absorption lines of neutral metals and of ions. The long-wavelength components of split absorption lines of BaII, SrII, TiII, and other strong lines with low excitation potentials for their lower levels are distorted by nearby emission lines. It is suggested that the short-wavelength components, whose locations correspond to the narrow velocity range V _r (blue) from approximately ?60 to ?70 km/s, are formed in a circumstellar envelope; one component of the D NaI doublet and the emission components of the FeII 6369.46 and 6432.68 Å ions are also formed there.