Cement Manufacture and the Environment: Part I: Chemistry and Technology

Hydraulic (chiefly portland) cement is the binding agent in concrete and mortar and thus a key component of a country's construction sector. Concrete is arguably the most abundant of all manufactured solid materials. Portland cement is made primarily from finely ground clinker, which itself is composed dominantly of hydraulically active calcium silicate minerals formed through high-temperature burning of limestone and other materials in a kiln. This process requires approximately 1.7 tons of raw materials per ton of clinker produced and yields about 1 ton of carbon dioxide (CO2) emissions, of which cal-cination of limestone and the combustion of fuels each con-tribute about half. The overall level of CO2 output makes the cement industry one of the top two manufacturing industry sources of greenhouse gases; however, in many countries, the cement industry's contribution is a small fraction of that from fossil fuel combustion by power plants and motor vehicles. The nature of clinker and the enormous heat requirements of its manufacture allow the cement industry to consume a wide variety of waste raw materials and fuels, thus providing the opportunity to apply key concepts of industrial ecology, most notably the closing of loops through the use of by-products of other industries (industrial symbiosis).
In this article, the chemistry and technology of cement manufacture are summarized. In a forthcoming companion ar-ticle (part II), some of the environmental challenges and op-portunities facing the cement industry are described. Because of the size and scope of the U.S. cement industry, the analysis relies primarily on data and practices from the United States.     

Assessment of CO 2 Emission Reduction Strategies for the Japanese Petrochemical Industry

Abstract: This article analyzes the possibilities for reducing carbon dioxide (CO₂) emissions in the life cycle of Japanese petrochemicals, focusing primarily on the nonenergy use of fossil fuels. For this purpose a linear programming model called CHEAP (CHemical industry Environmental strategy Analysis Program) has been developed. The results show a moderate autonomous growth of emissions by 5% in the period 2000 to 2020, if it is assumed that no new technology is introduced and demand (measured in physical units) increases 1% per year, on average. However, if it is assumed that ongoing technology development succeeds, emissions in 2020 may decrease by 5% from 2000 levels (a decrease of 10% compared to the case that assumes no new technology). This is a significant contribution to emission reduction. According to this model, a further emission reduction by 10% in 2020 is possible but costly as it requires emission reduction incentives of up to 10,000 yen per ton CO₂ (approximately 100 US/ton). The use of biomass feed-stocks, waste recycling, energy recovery from waste and gas-based co-generation are the main strategies for achieving this emission reduction.     

Saving Energy versus Saving Materials

To reduce energy consumption and carbon dioxide (CO₂) emissions in housing construction, the energy-intensive processes and life-cycle stages should be identified and integrated. The environmental impact of vertically integrated factory-built homes (VIHs) constructed with increased material inputs in Japan's northern island of Hokkaido was assessed using life-cycle inventory (LCI) analysis methods. Manufacturing process energy and CO₂ intensities of the homes were evaluated based on the material inputs. They were compared with those of a counterpart home hypothetically built using the vertically integrated construction methods, but in accordance with the specifications of a less material-intensive conventional home (CH) in Hokkaido today. Cumulative household energy consumption and CO₂ emissions were evaluated and compared with those of the production stages. The annual household energy consumption was compared among a VIH, a CH, and an average home in Hokkaido. The energy intensity of the VIH was 3.9 GJ production energy per m² of floor area, 59% higher than that of the CH. Net CO₂ emissions during VIH manufacturing processes were 293 kg/m², after discounting the carbon fixation during tree growth. The cumulative use-phase household energy consumption and CO₂ emissions of a VIH will exceed energy consumption and CO₂ emissions during the initial production stage in less than six years. Although VIHs housed 21% more residents on average, the energy consumption per m2 was 17% lower than that of a CH. This may indicate that using more materials initially can lead to better energy efficiency.     

Western European Materials as Sources and Sinks of CO2

Materials use is an important factor influencing carbon dioxide (CO₂) emissions because significant amounts of carbon dioxide are released during the production of materials from natural resources, and because products and wastes can function as important sinks for CO₂. This article analyzes the impact of Western European materials use on CO₂ emissions. The material flows for steel, cement, petrochemicals, and wood products are analyzed in more detail. The analysis shows that particular characteristics of the materials system must be considered in the development of emission reduction strategies. It is important to select a relatively closed system for policymaking, as in Western Europe, in order to prevent unwanted transboundary effects. The materials stored in the form of products, and the net exports of materials, products, and waste limit the potential of a recycling strategy. Carbon storage in products and waste disposal sites is significant both for synthetic and natural organic materials, but is not accounted for in natural organic materials in current emissions statistics. Accordingly the emissions accounting practices should be modified to reflect the storage of such materials.     

Enzymatic deconstruction of xylan for biofuel production

The combustion of fossil-derived fuels has a significant impact on atmospheric carbon dioxide (CO₂) levels and correspondingly is an important contributor to anthropogenic global climate change. Plants have evolved photosynthetic mechanisms in which solar energy is used to fix CO₂ into carbohydrates. Thus, combustion of biofuels, derived from plant biomass, can be considered a potentially carbon neutral process. One of the major limitations for efficient conversion of plant biomass to biofuels is the recalcitrant nature of the plant cell wall, which is composed mostly of lignocellulosic materials (lignin, cellulose, and hemicellulose). The heteropolymer xylan represents the most abundant hemicellulosic polysaccharide and is composed primarily of xylose, arabinose, and glucuronic acid. Microbes have evolved a plethora of enzymatic strategies for hydrolyzing xylan into its constituent sugars for subsequent fermentation to biofuels. Therefore, microorganisms are considered an important source of biocatalysts in the emerging biofuel industry. To produce an optimized enzymatic cocktail for xylan deconstruction, it will be valuable to gain insight at the molecular level of the chemical linkages and the mechanisms by which these enzymes recognize their substrates and catalyze their reactions. Recent advances in genomics, proteomics, and structural biology have revolutionized our understanding of the microbial xylanolytic enzymes. This review focuses on current understanding of the molecular basis for substrate specificity and catalysis by enzymes involved in xylan deconstruction.     

A model for photosynthesis and photorespiration in C3 plants based on the biochemistry and stoichiometry of the pathways

Abstract. A model is developed for photosynthesis and photorespiration in C₃ plants, using an equation for the multisubslrate ordered reaction of ribulose 1,5-bisphosphalc carboxylase-oxygenase (Farazdaghi & Edwards, 1988). The model examines net CO₂ fixation with O₂ inhibition, and mutual inhibition when equilibrium exists between carboxylation and oxygenation (at the CO₂ compensation point). It is based on the stoichiometry of energy requirements and O₂, and CO₂ exchange in the cycles, the quantum efficiency for RuBP generation, the maximum capacity for RuBP generation, the carboxylation efficiency with respect to [CO₂], and the oxygenation efficiency with respect to [O₂]. With increasing concentrations of CO₂ above the CO₂ compensation point, decreasing quantum flux density, or decreasing O₂, simulations show that the rate of photorespiration progressively decreases. The two components of O₂ inhibition of photosynthesis change disproportionately with increasing CO₂ concentration. According to the model, the energy utilized during photosynthesis at the CO₂ compensation point is about half that under atmospheric conditions.     

Wood composition and energy content in a poplar short rotation plantation on fertilized agricultural land in a future CO2 atmosphere

To study the influence of elevated CO₂ and nitrogen (N) fertilization on wood properties and energy, Populus × euramericana trees were exposed to ambient CO₂ (about 370 μmol mol⁻¹ CO₂) or elevated CO₂ (about 550 μmol mol⁻¹ CO₂) using Free Air CO₂ Enrichment (FACE) technology in combination with two N levels. Elevated CO₂ was maintained for 5 years. After three growing seasons, the plantation was coppiced, one half of each experimental plot was fertilized and secondary sprouts were harvested after two growing seasons. Fourier transform infrared (FT-IR) spectra of wood revealed significant effects of both elevated CO₂ and N fertilization on wood chemistry, in particular, significant increases in lignin and decreases in N content. These results were corroborated by chemical analysis. Neither elevated CO₂ nor N fertilization affected the calorific value of wood, which was 19.3 MJ kg⁻¹. N fertilization enhanced the energy production per land area by 16–69% because of higher aboveground woody biomass production than on nonfertilized land. Estimates indicate that high yielding poplar short rotation cultivation may significantly contribute as an alternative feedstock for energy production.     

Elevated CO2 concentration, nitrogen use, and seed production in annual plants

Elevated atmospheric CO₂ concentration ([CO₂]) stimulates seed mass production in many species, but the extent of stimulation shows large variation among species. We examined (1) whether seed production is enhanced more in species with lower seed nitrogen concentrations, and (2) whether seed production is enhanced by elevated [CO₂] when the plant uses more N for seed production. We grew 11 annuals in open top chambers that have different [CO₂] conditions (ambient: 370 μmol mol⁻¹, elevated: 700 μmol mol⁻¹). Elevated [CO₂] significantly increased seed production in six out of 11 species with a large interspecific variation (0.84–2.12, elevated/ambient [CO₂]). Seed nitrogen concentration was not correlated with the enhancement of seed production by elevated [CO₂]. The enhancement of seed production was strongly correlated with the enhancement of seed nitrogen per plant caused by increased N acquisition during the reproductive period. In particular, legume species tended to acquire more N and produced more seeds at elevated [CO₂] than non-nitrogen fixing species. Elevated [CO₂] little affected seed [N] in all species. We conclude that seed production is limited primarily by nitrogen availability and will be enhanced by elevated [CO₂] only when the plant is able to increase nitrogen acquisition.     

Accumulation and utilization of triacylglycerol and polysaccharides in Liposcelis bostrychophila (Psocoptera, Liposcelididae) selected for resistance to carbon dioxide

Abstract: Two populations of the psocid, Liposcelis bostrychophila Badonnel, were exposed to two CO₂-enriched atmospheres (35% CO₂ + 21% O₂, and 55% CO₂ + 21% O₂, balance N₂) for 30 generations. Controls were reared in normal atmospheres. The reserves of triacylglycerol and polysaccharides were evaluated in adults of the two experimental and the control populations in generations F₁₅ and F₃₀. The utilization rate of triacylglycerol and polysaccharides in the CO₂-enriched atmospheres were also determined in generation F₃₀. The results indicated that the reserves of triacylglycerol and polysaccharides increased significantly during selection for CO₂ resistance; the higher the resistance level, the greater the reserves. Exposure of these populations to controlled atmosphere was associated with a steady utilization of the reserves. By contrast, the unselected population responded to controlled atmospheres by accelerated utilization of triacylglycerol and polysaccharides. Comparison of the utilization rates during CO₂ exposure showed that triacylglycerol is the main energy source, and polysaccharides contribute to metabolic energy supply only to a small extent.     

Surfactants Based on Renewable Raw Materials

Under the European Commission's European Climate Change Programme, a group of experts studied the possibilities of using more renewable raw materials as chemical feedstock and assessed the related potential for greenhouse gas (GHG) emission reduction. Surfactants were among the products studied. Surfactants are currently produced from both petro-chemical feedstocks and renewable resources (oleochemical surfactants). Assuming, in a first step, that total surfactant production in the European Union remains constant until 2010, it was estimated that the amount of oleochemical surfactants could be increased from about 880 kilotons (kt) in 1998 to approximately 1, 100 kt in 2010 (an increase of 24%). This substitution reduces the life-cycle CO₂ emissions from surfactants by 8%; the theoretical maximum potential for total substitution is 37%. Because the surfactant market is expected to grow, the avoided emissions will probably exceed 8% of the current life-cycle CO₂ emissions from surfactants. If compared to the CO₂ emissions from the total industrial sector and, even more so, if compared to the total economy, the relative savings are much lower (0.02% to 0.09%). This leads to the conclusion that the increased production and use of biobased surfactants should be part of an overall GHG emission reduction strategy consisting of a whole range of measures addressing both energy demand and supply. This article also discusses policies and measures designed to increase the use of biobased surfactants.     

Photosynthetic biomass and H2 production by green algae: from bioengineering to bioreactor scale-up

The development of clean borderless fuels is of vital importance to human and environmental health and global prosperity. Currently, fuels make up approximately 67% of the global energy market (total market = 15 TW year⁻¹) ( Hoffert et al. 1998 ). In contrast, global electricity demand accounts for only 33% ( Hoffert et al. 1998 ). Yet, despite the importance of fuels, almost all CO₂ free energy production systems under development are designed to drive electricity generation (e.g. clean-coal technology, nuclear, photovoltaic, wind, geothermal, wave and hydroelectric). In contrast, and indeed almost uniquely, biofuels also target the much larger fuel market and so in the future will play an increasingly important role in maintaining energy security ( Lal 2005 ). Currently, the main biofuels that are at varying stages of development include bio-ethanol, liquid carbohydrates [e.g. biodiesel or biomass to liquid (BTL) products], biomethane and bio-H₂. This review is focused on placing bio-H₂ production processes into the context of the current biofuels market and summarizing advances made both at the level of bioengineering and bioreactor design.     

The significance of differences in the mechanisms of photosynthetic acclimation to light, nitrogen and CO2 for return on investment in leaves

1. We report changes in photosynthetic capacity of leaves developed in varying photon flux density (PFD), nitrogen supply and CO₂ concentration. We determined the relative effect of these environmental factors on photosynthetic capacity per unit leaf volume as well as the volume of tissue per unit leaf area. We calculated resource-use efficiencies from the photosynthetic capacities and measurements of leaf dry mass, carbohydrates and nitrogen content.
2. There were clear differences between the mechanisms of photosynthetic acclimation to PFD, nitrogen supply and CO₂. PFD primarily affected volume of tissue per unit area whereas nitrogen supply primarily affected photosynthetic capacity per unit volume. CO₂ concentration affected both of these parameters and interacted strongly with the PFD and nitrogen treatments.
3. Photosynthetic capacity per unit carbon invested in leaves increased in the low PFD, high nitrogen and low CO₂ treatments. Photosynthetic capacity per unit nitrogen was significantly affected only by nitrogen supply.
4. The responses to low PFD and low nitrogen appear to function to increase the efficiency of utilization of the limiting resource. However, the responses to elevated CO₂ in the high PFD and high nitrogen treatments suggest that high CO₂ can result in a situation where growth is not limited by either carbon or nitrogen supply. Limitation of growth at elevated CO₂ appears to result from internal plant factors that limit utilization of carbohydrates at sinks and/or transport of carbohydrates to sinks.     

Respiration in a future, higher-CO2 world

Abstract. Apart from its impact on global warming, the annually increasing atmospheric [CO₂] is of interest to plant scientists primarily because of its direct influence on photosynthesis and photorespiration in C₃ species. But in addition, 'dark' respiration, another major component of the carbon budget of higher plants, may be affected by a change in [CO₂] independent of an increase in temperature. Literature pertaining to an impact of [CO₂] on respiration rate is reviewed. With an increase in [CO₂], respiration rate is increased in some cases, but decreased in others. The effects of [CO₂] on respiration rate may be direct or indirect. Mechanisms responsible for various observations are proposed. These proposed mechanisms relate to changes in: (1) levels of nonstructural carbohydrates, (2) growth rate and structural phytomass accumulation, (3) composition of phytomass, (4) direct chemical interactions between CO₂ and respiratory enzymes, (5) direct chemical interactions between CO₂ and other cellular components, (6) dark CO₂ fixation rate, and (7) ethylene biosynthesis rate. Because a range-of (possibly interactive) effects exist, and present knowledge is limited, the impact of future [CO₂] on respiration rate cannot be predicted. Theoretical considerations and types of experiments that can lead to an increase in the understanding of this issue are outlined.     

Effects of elevated CO2-grown loblolly pine needles on the growth, consumption, development, and pupal weight of red-headed pine sawfly larvae reared within open-topped chambers

Seedlings of loblolly pine, Pinus taeda , were grown in open-topped chambers under four levels of CO₂: two ambient and two elevated. Larvae of the red-headed pine sawfly, Neodiprion lecontei , were reared from early instar to pupation, primarily on branches within chambers. Larval growth and mortality were assessed and leaf phytochemistry samples of immature and mature leaves collected weekly. Mature leaves grown under elevated CO₂ had significant reductions in leaf nitrogen and increases in non-structural carbohydrate contents, resulting in foliage being a poorer food source for larvae, i.e. higher carbohydrate:nitrogen ratio. Nutritional constituents of immature needles were unaffected by seedling CO₂ treatment. Volatile mono- and sesquiterpenes were unrelated to plant CO₂ treatments for either leaf age class. Larval consumption of immature needles significantly increased on seedlings grown under CO₂ enrichment, while mature needle consumption was not different between the treatments. The average weight gain per larva significantly declined in late instar larvae consuming elevated CO₂-grown needles. In spite of this reduced growth, neither the days to pupation nor pupal weights were different among the CO₂ treatments. This study suggests that enriched CO₂-induced alterations in pine needle phytochemistry can affect red-headed pine sawfly performance. However, compensatory measures by larvae, such as choosing to consume more nutritious immature needles, apparently helps offset enriched CO₂-induced reductions in the leaf quality of mature needles.     

A parametric study of the destruction efficiency of Bacillus spores in low pressure oxygen-based plasmas

The destruction of Bacillus spores in oxygen-based plasmas sustained in the millitorr pressure range has been studied as functions of various biological and plasma parameters, namely Bacillus species, surface concentration of spores, treatment temperature, and gas composition. In an oxygen plasma, Bacillus stearothermophilus appears less plasma-resistant than the other spores tested. Oxygen, H₂O₂ and chiefly CO₂ plasmas are clearly shown to be much more efficient in destroying Bacillus subtilis spores than pure argon plasma. The bacterial surface concentration on the spore carriers and the treatment temperature also lead to significant variations in the destruction efficiency of spores when using CO₂ plasma.     

Growth in elevated CO2 enhances temperature response of photosynthesis in wheat

The temperature dependence of C₃ photosynthesis may be altered by the growth environment. The effects of long-term growth in elevated CO₂ on photosynthesis temperature response have been investigated in wheat ( Triticum aestivum L.) grown in controlled chambers with 370 or 700 μmol mol⁻¹ CO₂ from sowing through to anthesis. Gas exchange was measured in flag leaves at ear emergence, and the parameters of a biochemical photosynthesis model were determined along with their temperature responses. Elevated CO₂ slightly decreased the CO₂ compensation point and increased the rate of respiration in the light and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) V_cmax, although the latter effect was reversed at 15°C. With elevated CO₂, J_max decreased in the 15–25°C temperature range and increased at 30 and 35°C. The temperature response (activation energy) of V_cmax and J_max increased with growth in elevated CO₂. CO₂ enrichment decreased the ribulose 1,5-bisphosphate (RuBP)-limited photosynthesis rates at lower temperatures and increased Rubisco- and RuBP-limited rates at higher temperatures. The results show that the photosynthesis temperature response is enhanced by growth in elevated CO₂. We conclude that if temperature acclimation and factors such as nutrients or water availability do not modify or negate this enhancement, the effects of future increases in air CO₂ on photosynthetic electron transport and Rubisco kinetics may improve the photosynthetic response of wheat to global warming.     

Are legume‐feeding herbivores buffered against direct effects of elevated carbon dioxide on host plants? A test with the sulfur butterfly,Colias philodice

When grown under elevated atmospheric carbon dioxide (CO₂), leaf nitrogen content decreases less for legumes than for nonlegume C₃ plants. Given that elevated CO₂ adversely affects insect herbivores primarily through dilution of plant nitrogen, it is reasonable to expect that legume-feeding herbivores will be relatively buffered against CO₂-induced reduction in performance. However, despite their ecological and economic importance, very few studies have addressed the effects of elevated CO₂ on legume-feeding herbivores. Unlike the responses of the vast majority of nonlegume C₃ plants, when the legumes Trifolium pratense and Melilotus alba were grown under elevated (742 ppm) CO₂, leaf nitrogen and carbon contents and C : N ratios did not change. For Colias philodice larvae fed T. pratense , elevated CO₂ had little or no effect on consumption, digestion, or conversion of whole food or nitrogen and, consequently, no effect on growth rate, instar duration, or pupal weight. For larvae fed M. alba , elevated CO₂ had little or no effect on consumption of whole food or nitrogen, increased digestion but decreased conversion of both and, consequently, had no effect on growth rate, instar duration or pupal weight. These results suggest that, relative to herbivores of nonlegume C₃ plants, legume-feeding herbivores will be less affected as atmospheric CO₂ continues to rise.     

The impact of elevated ozone and carbon dioxide on young Acer saccharum seedlings

The effects of high O₃ (200 nl l⁻¹ during the light period) and high CO₂ (650 μl l⁻¹ CO₂, 24 h a day) alone and in combination were studied on 45-day-old sugar maple ( Acer saccharum Marsh.) seedlings for 61 days in growth chambers. After 2 months of treatment under the environmental conditions of the experiment, sugar maple seedlings did not show a marked response to the elevated CO₂ treatment: the effect of high CO₂ on biomass was only detected in the leaves which developed during the treatment, and assimilation rate was not increased. Under high O₃ at ambient CO₂, assimilation rate at days 41 and 55 and Rubisco content at day 61 decreased in the first pair of leaves; total biomass was reduced by 43%. In these seedlings large increases (more than 2-fold) in glucose 6-phosphate dehydrogenase (G6PDH, EC 1.1.1.49) activity and in anaplerotic CO₂ fixation by phosphoenolpyruvate carboxylase (PEPC, EC 4.1.1.31) were observed, suggesting that an enhanced reducing power and carbon skeleton production was needed for detoxification and repair of oxidative damage. Under high O₃ at elevated CO₂, a stimulation of net CO₂ assimilation was observed after 41 days but was no longer observed at day 55. However, at day 61, the total biomass was only reduced by 21% and stimulation of G6PDH and PEPC was less pronounced than under high O₃ at ambient CO₂. This suggests that high CO₂ concentration protects, to some extent, against O₃ by providing additional carbon and energy through increased net assimilation.     

Growth and physiological responses of canola (Brassica napus) to UV-B and CO2 under controlled environment conditions

Few studies have investigated the interaction of ultraviolet (UV)-B radiation and CO₂ concentration on plants. We studied the combined effects of UV-B radiation and CO₂ concentration on canola ( Brassica napus cv. 46A65) under four growth conditions – ambient CO₂ with UV-B (control), elevated CO₂ with UV-B, ambient CO₂ without UV-B, and elevated CO₂ without UV-B – to determine whether the adverse effects of UV-B are mitigated by elevated CO₂. Elevated CO₂ significantly increased plant height and seed yield, whereas UV-B decreased them. Elevated CO₂ ameliorated the adverse effects of UV-B in plant height. UV-B did not affect the physical characteristics of leaf but CO₂ did. Certain flower and fruit characteristics were affected negatively by UV-B and positively by CO₂. UV-B did not affect net photosynthesis, transpiration and stomatal conductance but decreased water use efficiency (WUE). Elevated CO₂ significantly increased net photosynthesis and WUE. Neither UV-B nor CO₂ affected chlorophyll (Chl) fluorescence. UV-B significantly decreased Chl b and increased the ratio of Chl a / b . Elevated CO₂ decreased only the ratio of Chl a / b . UV-B significantly increased UV-absorbing compounds while CO₂ had no effect on them. Both UV-B and CO₂ significantly increased epicuticular wax content. Many significant relationships were found between morphological, physiological, and chemical parameters. This study showed that elevated CO₂ can partially ameliorate some of the adverse effects of UV-B radiation in B . napus .     

Elevated atmospheric CO2 alters wood production, wood quality and wood strength of Scots pine (Pinus sylvestris L) after three years of enrichment

Scots pine ( Pinus sylvestris L.) trees were grown in open top chambers for three years under ambient and elevated CO₂ concentrations. The trees were aged 3 y at the beginning of the CO₂ exposure, and the effects of the treatment on total stem volume, stem wood biomass, wood quality and wood anatomy were examined at the end of the exposure. The elevated CO₂ treatment lead to a 49% and 38% increase in stem biomass and stem wood volume, respectively. However, no significant effects of the elevated CO₂ treatment on wood density were observed, neither when green wood density was estimated from stem biomass and stem volume, nor when oven-dry wood density was measured on small wood samples. Under elevated CO₂ significantly wider growth rings were observed. The effect of elevated CO₂ on growth ring width was primarily the result of an increase in earlywood width. Wood compression strength decreased under elevated CO₂ conditions, which could be explained by significantly larger tracheids and the increased earlywood band, that has thinner walls and larger cavities. A significant decrease of the number of resin canals in the third growth ring was observed under the elevated treatment; this might indicate that trees produced and contained less resin, which has implications for disease and pest resistance. So, although wood volume yield in Scots pine increased significantly with elevated CO₂ after three years of treatment, wood density remained unchanged, while wood strength decreased. Whilst wood volume and stem biomass production may increase in this major boreal forest tree species, wood quality and resin production might decrease under future elevated CO₂ conditions.