Hydrotalcite-like solid solutions with variable SO 4 2− and CO 3 2− contents at 50° C

Hydrotalcite-like solid solutions have been synthesized by coprecipitation in basic solutions with variable SO ₄ ^2? /CO ₃ ^2? ratios. Chemical determination of CO ₃ ^2? in the interlayer was impossible because of the presence of minor hydromagnesite. SO ₄ ^2? was determined both by chemical analysis and X-ray photoelectron spectroscopy (XPS), the two methods giving similar results. A Raman spectrometry gave additional data on the SO ₄ ^2? /CO ₃ ^2? ratio. Then, the stoichiometry of the anionic interlayers, X _s , X _c , and X _OH were determined, and the influence of X _s on the c′ parameter (increasing from c′=7.97 Å to c′=8.63 Å between X _s =0 and X _s =1) was characterized. In addition, a partitioning curve of SO ₄ ^2? and CO ₃ ^2? between aqueous solutions and hydrotalcite-like compounds was established. Its general shape strongly suggests a miscibility gap between a sulfate-rich end and a carbonate-rich solid solution (maximum SO ₄ ^2? /CO ₃ ^2? about 0.2). This result explains why most of the hydrotalcites synthesized during experimental alteration of basaltic glasses by sea-water (a sulfate-rich solution) are CO ₃ ^2? -rich solid solutions.     

硫酸参与的长江流域岩石化学风化速率与大气CO2消耗

流域的岩石化学风化过程是全球碳循环中的重要环节。以往的流域水化学碳汇通量估算大多是基于碳酸的风化作用。而实际上,硫酸和碳酸一样,也参与了流域碳元素的地球化学循环,从而对全球碳循环过程产生影响。长江流域水体近几年出现酸化现象,大部分河段SO42-和Ca2+含量增高,其对应的岩石风化过程和大气CO2消耗速率也发生变化。文章对长江干流及主要支流2013年不同季节的离子组成进行监测,利用水化学平衡法和Galy估算模型,对长江流域岩石化学风化速率和CO2消耗通量进行了估算,对硫酸参与下的长江流域岩石风化和碳循环过程进行了分析。结果表明,长江流域水体离子主要来源于硅酸盐岩风化和碳酸盐岩风化。其中碳酸盐岩风化对河水离子贡献率为92%。在硅酸盐岩广泛分布的赣江流域,碳酸盐岩风化离子贡献也达85%。分析表明,硫酸参与了长江流域的岩石风化过程,对水体中离子产生一定影响。硫酸的参与加快了碳酸盐岩的化学风化速率,平均提高约30%,但是使流域大气CO2消耗速率降低。在不考虑蒸发岩溶蚀作用下,平均从516×103 mol/km2·a降至356×103 mol/km2·a,降低约31%。在各支流中,硫酸对乌江流域碳酸盐岩的风化和碳循环的影响最大,而对雅砻江的影响最小,这与乌江流域的含煤地层、矿床硫化物及大气酸沉降有关。     

从树轮纤维素δ13C序列看树木生长对大气CO2浓度变化的响应

在新疆昭苏树轮碳同位素组成研究的基础上，初步分析了近280a以来云杉内外CO2浓度比（Ci/Ca)，云杉内部CO2浓度（Ci)和水分利用效率（A／g)的变化，结果表明，在整个分析时段内Ci/Ca相对恒定在0．52左右，暗示树木生长对大气CO2浓度升高的基本响应策略；Ci和A/g都有较明显的升高趋势，说明可能有更多的碳被固定在树木之中，进一步分析表明，它们的这种趋势与大气CO2浓度变化有关，从另一个侧面证明了人类活动释放的碳有一部分被树木吸收。     

丁二酸桥联双核铜Cu(C_3N_2H_4)_2(C_4H_5O_4)_2晶体的超分子结构及形貌特征

用XRD,SEM和TEM研究新型配合物Cu(C3N2H4)2(C4H5O4)2的超分子结构和微观形貌,并对新型晶体的平衡外形进行模拟计算,结果表明:该配合物分子具有丁二酸桥联的双核铜结构,中心铜离子处在2个咪唑和4个丁二酸以单齿配位组成的八面体中心,在ab平面,分子中有十四元大环,环内Cu(1)-Cu(2)原子间距为0.8031nm,C(2)-C(2′)为0.4183nm;在ac平面,沿着[010]方向分子内呈现凹的六边形纳米级孔洞;沿[100]方向分子依靠弱的氢键作用,层状堆积成三维超分子结构。此外,随着丁二酸的碳链沿[001]方向无限延伸,形成以铜离子为交叉中心的带状拓扑构型。SEM观察到晶体表面形成有明显的凹坑,区域呈现层状阶梯,说明晶体在(100)面遵照台阶-扭折模型呈层状生长结晶。TEM微区形貌像显示晶体存在条纹和缺陷结构,整体保持柱状构型,这与模拟的晶体平衡外形呈柱状一致。模拟结果表明晶体最易外显晶面为(100)面,外显比例达41.247%,这与晶体超分子层沿[100]方向通过氢键作用堆积,键作用力较弱密切相关。     

A new partial substitution mechanism of CO 3 2− /CO3OH3− and SiO 4 4− for the PO 4 3− group in hydroxyapatite from the Kaiserstuhl alkaline complex (SW-Germany)

Based on a detailed mineral-chemical investigation of apatite from a series of carbonatites and associated silicate volcanic rocks of the Kaiserstuhl tertiary alkaline volcanic centre, evidence for a new substitution mechanism was found within the hydroxyapatite group, yielding the following simplified formula: (Ca, Sr, LREE)₁₀(SiO₄)_x(CO₃)_x(PO₄)_6–2x(OH, F)₂ with 03 ^2– and SiO ₄ ^4– for PO ₄ ^3– ; however, excess charge may be subsequently adjusted by CO₃OH^3– partly accompanied by the REE in the Ca site.     

The experimental investigation of the reactions MnCO3+SiO2=MnSiO37#x002B;CO2 and MnSiO3+MnCO3=Mn2SiO4+CO2 in CO2/H2O gasmixtures at a total pressure of 500 bars

The equilibrium constants for the reaction (2) Rhodochrosite + Quartz=Pyroxmangite+CO₂ obtained are:logK(₂)(bars)= $$\begin{gathered}{\text{log}}f_{co_2 } = - \frac{{(9862 \pm 102)}}{T} \hfill \\+ (15.887 \pm 0.220) + (0.1037 \pm 0.0020)\frac{{P - 1}}{T} \hfill \\\end{gathered} $$ and for the reaction (3) Rhodochrosite+Pyroxmangite=Tephroite+CO₂: logK(₃)(bars)= $$\begin{gathered}{\text{log}}f_{co_2 } = - \frac{{(6782 \pm 205)}}{T} \hfill \\+ (11.296 \pm 0.304) + (0.0835 \pm 0.0030)\frac{{P - 1}}{T} \hfill \\\end{gathered} $$ The present data lie within reasonable limits of error of the values calculated from previous experimental results at P _tot = 2000 bars.     

Stabilization of complex ions by the crystal field: CO 3 2− , NO 3 − , O 3 − , [(OH)4]4−, [(OH)3F]4−, [(OH)2F2]4−

According to Koopmans' theorem, only the electrons associated with molecular levels of negative energy are stable. Many ions which cannot exist in the isolated state because certain occupied levels are positive, become stable in crystals under the stabilization effect arising from the crystal field. As examples, we have studied CO ₃ ^2? in calcite, NO ₃ ^? in NaNO₃, and several natural limpurities: O ₃ ^? in fluorite, [(OH)₄]^4?, [(OH)₃F]^4? and [(OH)₂F₂]^4? in zircon and thorite, by means of the molecular self-consistent field, the crystal field being simulated by point charges. As expected, all the energies corresponding to the occupied levels are negative within the crystal field, contrary to what occurs in the isolated state. Informations concerning the structure and the size of the critical germ are obtained for CaCO₃ and NaNO₃.     

Strain development in unconfined coals exposed to CO2, CH4 and Ar: Effect of moisture

Field experiments and laboratory studies have shown that swelling of coal takes place upon contact with carbon dioxide at underground pressure and temperature conditions. Understanding this swelling behavior is crucial for predicting the performance of future carbon dioxide sequestration operations in unminable coal seams conducted in association with methane production. Swelling is believed to be related to adsorption on the internal coal surface. Whereas it is well established that moisture influences the sorption capacity of coal, the influence of water on coal swelling is less well-defined. This paper presents the results of laboratory experiments to investigate the effect of moisture on coal swelling in the presence of carbon dioxide, methane and argon. Strain development of an unconfined sample of about 1.0–1.5 mm³ at 40 °C and 8 MPa (and at other pressures) was observed in an optical cell under a microscope as a function of time. Both air dried and moisturized samples were used. Results confirmed different swelling behaviors of coal with different substances: carbon dioxide leads to higher strain than methane, while exposure to argon leads to very little swelling. The experiments on moisturized samples seem to confirm the role of moisture as a competitor to gas molecules for adsorption sites. Adsorption of water could also explain the observed swelling due to water uptake at atmospheric pressure. A re-introduction of carbon dioxide, after intermediate gas release, results in higher strains which indicate a drying effect of the carbon dioxide on the coal. The results of this study show that the role of water cannot be ignored if one wants to understand the fundamental processes that are taking place in enhanced coalbed methane operations.     

A rapid method for preparing low volume CH4 and CO2 gas samples for 14C AMS analysis

¹⁴C measurements of CH₄ in environmental samples (e.g. soil gas, lake water, gas hydrates) can advance understanding of C cycling in terrestrial and marine systems. The measurements are particularly useful for detecting the release of old C from climate sensitive environments such as peatlands and hydrate fields. However, because ¹⁴C CH₄ measurements tend to be complex and time consuming, they are uncommon. Here, we describe a novel vacuum line system for the preparation of CH₄ and CO₂ from environmental samples for ¹⁴C analysis using accelerator mass spectrometry (AMS). The vacuum line is a flow-through system that allows rapid preparation of samples (1 h for CH₄ and CO₂, 30 min for CH₄ alone), complete separation of CH₄ and CO₂ and is an easy addition to multipurpose CO₂ vacuum lines already in use. We evaluated the line using CH₄ and CO₂ standards with different ¹⁴C content. For CH₄ and CO₂, respectively, the total line blank was 0.4 ± 0.2 and 1.4 ± 0.6 μg C, the ¹⁴C background 51.1 ± 1.2 and 48.4 ± 1.5 kyr and the precision (based on pooled standard deviation) 0.9‰ and 1.3‰. The line was designed for sample volumes of ca. 180 ml containing 0.5–1% CH₄ and CO₂, but can be adjusted to handle lower concentration and larger volume samples. This rapid and convenient method for the preparation of CH₄ and CO₂ in environmental samples for ¹⁴C AMS analysis should provide more opportunities for the use of ¹⁴C CH₄ measurements in C cycle studies.     

Strategies for addressing climate change on the industrial level: affecting factors to CO2 emissions of energy-intensive industries in China

Urban earthquake disaster prevention is regarded as an integrated systematic engineering. Urban earthquake disaster prevention system is made up of all the earthquake disaster prevention activities. The concept and composition of urban earthquake disaster prevention system periphery were presented based on system periphery theory. A seismic risk-control mechanism model of system periphery was deduced using exchange rate of periphery as a dependent variable, and an observability–controllability model of system periphery was established and crystallized in its application to the quantitative analysis of practice problem. The input sets of urban earthquake disaster prevention system are determined as the maximum earthquake magnitude happened in or around the city, the measurable earthquake frequency, population density and fixed assets density. The inside state sets of urban earthquake disaster prevention system are determined as disaster resistant ability of buildings, disaster resistant ability of lifelines and investment dynamics in disaster prevention per urban built-up area. The system output is urban seismic risk. The calculative results show the model presented in this study can analyze the influence of system periphery intensity and inside state on seismic risk and can control urban seismic risk by adjusting the parameters of system periphery, the system inside state and human influence intensity.     

A multi-methodological approach to determine CO2 and CH4 fluxes and concentrations in solid waste disposal

The municipal solid waste （MSW） landfills are the significant sources of atmospheric contamination, due to biogas production by anaerobic decomposition of organic matter via bacterial activity. Biogas released from landfills is commonly composed of a mixture of methane （55%-60%） and carbon dioxide （40%-45%）, with minor contents of N2, H2, CO and traces of toxic and bad smelling inorganic and organic compounds. Particular attention has to be paid to CH4 and CO2 because of their liability for the greenhouse effect. Presently, the U.S. methane emission from landfills is considered to be about 25% of the total methane released to the atmosphere. Accordingly, field measurements should be planned in order to verify and, eventually, optimize the amount of gases released from waste disposals to the atmosphere. Simultaneous measurements of methane and carbon dioxide fluxes are an effective tool to better evaluate： （1） the amount of biogas released, （2） the real efficiency of the impervious cover, and （3） the presence of anomalous degassing zones or of newly formed fractures. Static closed-chamber methods for CH4 and CO2 flux measurements have been developed and used in both natural and artificial systems. Furthermore, portable gas-chromatographers equipped with flame ionization detector （FID） and accumulation chamber connected to infrared detectors （IR） .have been utilized for measuring CH4 and CO2 fluxes, respectively. This paper deals with a detailed investigation that combines （1） CH4 and CO2 flux measurements from solid waste disposal and surrounding areas （determined by an accumulation chamber equipped with two IR detectors, respectively）, （2） chemical composition of soil and piezometer gases （collected in pre-evacuated glass tubes and analyzed by gas-chromatography）, and （3） CO2 linear concentration measurements on optical air paths with IR laser devices. This multi-methodological approach was successfully applied to an active MSW in Tuscany （Central Italy）. The analytical results have shown that the CO2/CH4 ratios of the piezometer gases have large variations, likely related to the different stage of decomposition processes affecting the heterogeneous solid material of the waste landfill. Significant contents of light hydrocarbons and BTX were also detected.     

生物气CO2还原途径中碳同位素分馏作用研究及应用

地质历史中,CO2/H2还原产甲烷作用对生物气的形成具有十分重要的意义。中国柴达木盆地第四系生物气主要为CO2/H2还原型生物气。笔者以CO2/H2还原生气理论为指导,进行不同初始碳同位素值和不同赋存状态碳源的生物模拟实验,研究CO2/H2还原产气过程中发生的碳同位素分馏作用。实验结果表明,产物中δ13CH4值与底物的δ13C值呈很好的正相关关系;在反应母质过量的情况下,碳源的赋存状态可以影响产物甲烷的碳同位素组成。以游离形式CO2还原产生的甲烷δ13C值,相对于以HCO3-、CO23-离子形式产生的甲烷δ13C值轻。通过柴达木盆地东部第四系生物气田实例分析,探讨了该区生物气的主要底物CO2的来源及赋存状态,对评价盆地生物气资源和有利勘探区预测有重要的参考价值。     

Nature and role of CO2 in some hot and cold HCO3/Na/CO2-rich Portuguese mineral waters: a review and reinterpretation

 At the northern part of the Portuguese mainland, the upflow zone of several hot and cold HCO₃/Na/CO₂-rich mineral waters is mainly associated with important NNE–SSW faults. Several geochemical studies have been carried out on thermal and non-thermal hydromineral manifestations that occur along or near these long tectonic alignments. The slight chemical differences that exist between these meteoric hot and cold HCO₃/Na/CO₂-rich mineral waters seem to be mainly caused by CO₂. δ¹³C_(TIDC) values observed in these groundwaters range between –6.00 and –1.00‰ versus V-PDB (V denotes Vienna, the site of the International Atomic Energy Agency; PDB originates from the CaCO₃ of the rostrum of a Cretaceous belemnite, Belemnitella americana, collected in the Peedee formation of South Carolina, USA) indicating a deep-seated (mantle) origin for most of the CO₂. Nevertheless, in the case of the heavier δ¹³C_(TIDC) values, the contribution of metamorphic CO₂ or the dissolution of carbonate rock levels at depth cannot be excluded. Concerning the hot waters, the lack of a positive ¹⁸O-shift should be attributed to water-rock interaction in a low temperature environment, rather than to the isotopic influence of CO₂ on the δ¹⁸O-value of the waters. Received: 9 August 1999 · Accepted: 8 March 2000     

CO2, 13C/12C and H2O variability in natural basaltic glasses: a study comparing stepped heating and ftir spectroscopic techniques

A comparison of two independent techniques was used to assess the homogeneity of CO₂ and H₂O concentrations in a number of natural basaltic glasses. Variations in carbon concentration and isotopic ratio were determined by comparison of stepped heating data obtained in two different laboratories. Dissolved volatile concentrations were also obtained by stepped heating and Fourier Transform Infrared (FTIR) spectroscopy. Replicate stepped heating analyses of a mid-ocean ridge basaltic glass show that the concentration and ¹³C/¹²C of bulk magmatic and dissolved CO₂ vary by less than ±10% and ±0.5‰, respectively. A similar degree of correlation is observed for replicate stepped heating analyses of Mariana Trough glasses conducted in two different laboratories. Dissolved CO₂ concentrations determined by stepped heating also correlate well with concentrations measured by FTIR spectroscopy. The correspondence of results obtained in these experiments provide an upper limit to the degree of natural variation in concentrations and isotopic ratios of these volatiles in basaltic glasses and suggest that intrinsic, magmatic carbon has a relatively homogeneous distribution in these glasses. Water concentrations determined through extraction by heating and FTIR also show excellent agreement.     

Hydrogen bonding in basic copper salts: a spectroscopic study of malachite,Cu2(OH)2CO3, and brochantite,Cu4(OH)6SO4

Infrared and Raman spectra of the basic copper salts malachite, Cu₂(OH)₂CO₃, and brochantite, Cu₄(OH)₆SO₄, as well as of deuterated and ¹³C substituted samples are presented and discussed in terms of group theory and the hydrogen bonds present. The main results are that (i) the hydrogen donor strengths of the OH^? ions are strongly increased due to the very great synergetic effect of the copper ions, (ii) the acceptor strengths of the H-bond acceptor groups (SO₄ ^2-, CO₃ ^2-, and OH^? ions) are significantly modified by the linkage and coordination of the acceptor atoms — this complicates true assignment of the OH bands observed to the two and six different OH^? ions present in malachite and brochantite, respectively -, and (iii) the Cu — O stretching modes at 430–590 cm^?1 and 420–520 cm^?1 for malachite and brochantite, respectively, exhibit strong, partially covalent Cu — O bonding.     

Physical properties of selected block Argonne Premium bituminous coal related to CO2, CH4, and N2 adsorption

CO₂, CH₄, and N₂ adsorption and gas-induced swelling were quantified for block Blind Canyon, Pittsburgh #8 and Pocahontas Argonne Premium coals that were dried and structurally relaxed at 75 °C in vacuum. Strain measurements were made perpendicular and parallel to the bedding plane on ~ 7 × 7 × 7 mm³ coal blocks and gravimetric sorption measurements were obtained simultaneously on companion coal blocks exposed to the same gaseous environment. The adsorption amount and strain were determined after equilibration at P  ≤ 1.8 MPa. There is a strong non-linear correlation between strain and the quantity of gas adsorbed and the results for all gases and coals studied follow a common pattern. The dependence of the coal matrix shrinkage/swelling coefficient (C_gc) on the type and quantity of gas adsorbed is seen by plotting the ratio between the strain and the adsorbate concentration against the adsorbate concentration. In general, C_gc increases with increasing adsorbate concentration over the range of ~ 0.1 to 1.4 mmol/g. Results from the dried block coals are compared to CO₂ experiments using native coals with an inherent level of moisture as received. The amount of CO₂ adsorbed using native coals (assuming no displacement of H₂O by CO₂) is significantly less than the dried coals. The gas-induced strain (S) and adsorption amount (M) were measured as a function of time following step changes in CO₂, CH₄, and N₂ pressure from vacuum to 1.8 MPa. An empirical diffusion equation was applied to the kinetic data to obtain the exponent (n) for time dependence for each experiment. The data for all coals were pooled and the exponent (n) evaluated using an ANOVA statistical analysis method. Values for (n) near 0.5 were found to be independent on the coal, the gas or type of measurement (e.g., parallel strain, perpendicular strain, and gas uptake). These data support the use of a Fickian diffusion model framework for kinetic analysis. The kinetic constant k was determined using a unipore diffusion model for each experiment and the data were pooled for ANOVA analysis. For dry coal, statistically significant differences for k were found for the gases (CO₂ > N₂ > CH₄) and coals (Pocahontas >Blind Canyon > Pittsburgh #8) but not for the method of the kinetic measurement (e.g., strain or gas uptake). For Blind Canyon and Pittsburgh #8 coal, the rate of CO₂ adsorption and gas-induced strain for dry coal was significantly greater than that of the corresponding native coal. For Pocahontas coal the rates of CO₂ adsorption and gas-induced strain for dry and native coal were indistinguishable and may be related to its low native moisture and minimal amount of created porosity upon drying.     

Return of the coral reef hypothesis: basin to shelf partitioning of CaCO3 and its effect on atmospheric CO2

Differences in the rate of coral reef carbonate deposition from the Pleistocene to the Holocene may account for the Quaternary variation of atmospheric CO2. Volumes of carbonate associated with Holocene reefs require an average deposition rate of 2.0 x 10(13) mol/yr for the past 5 ka. In light of combined riverine, midocean ridge, and ground-water fluxes of calcium to the oceans of 2.3 x 10(13) mol/yr, the current flux of calcium carbonate to pelagic sediments must be far below the Pleistocene average of 1.2 x 10(13) mol/yr. We suggest that sea-level change shifts the locus of carbonate deposition from the deep sea to the shelves as the normal glacial-interglacial pattern of deposition for Quaternary global carbonates. To assess the impact of these changes on atmospheric CO2, a simple numerical simulation of the global carbon cycle was developed. Atmospheric CO2 as well as calcite saturation depth and sediment responses to these carbonate deposition changes are examined. Atmospheric CO2 changes close to those observed in the Vostok ice core, approximately 80 ppm CO2, for the Quaternary are observed as well as the approximate depth changes in percent carbonate of sediments measured in the Pacific Ocean over the same time interval.     

Synthetic bayleyite,Mg2[UO2(CO3)3]·18H2O: Thermochemistry,crystallography and crystal structure

Summary Thermochemistry, morphology, optical properties and crystal structure of synthetic bayleyite, Mg₂[UO₂(CO₃)₃]·18H₂O, monoclinic, have been studied. Incongruent melting at 55°, three steps of dehydration and two steps of decarboxylation have been found by thermochemic investigations. Morphology: Prisms along [001] with {100}, {110}, {210}, {001}, {401}, {021}, {211}, {111} and as the most important forms. Optical data:n =1.453,n =1.498,n =1.499, 2V _x =16°,Y=b,X c=11°. Crystal structure: Space groupP2₁/a,a=26.560(3),b=15.256(2),c=6.505(1) Å, =92.90(1)°,Z=4,R=0.029 for 5126 independent reflections measured with MoK -radiation. The structure is built up from isolated Mg(H₂O)₆ octahedra, UO₂(CO₃)₃ units and lattice water molecules, all held together by hydrogen bonds only.

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Synthetischer Bayleyit, Mg₂[UO₂(CO₃)₃]·18H₂O: Thermochemie, Kristallographie und Kristallstruktur

Zuseammenfasung Thermochemie, Morphologie, optische Eigenschaften und Kristallstruktur von Bayleyit, Mg₂[UO₂(CO₃)₃]·18H₂O, monoklin, wurden anhand künstlich hergestellter Kristalle untersucht. Durch thermochemische Untersuchung wurden inkongruentes Schmelzen bei 55°, eine dreistufige Wasserabgabe sowie eine zweistufige CO₂-Abgabe festgestellt. Morphologie: parallel zu [001] gestreckte Prismen mit {100}, {110}, {210}, {001}, {401}, {021}, {211}, {111}, und {311} als wichtigste Formen. Optische Daten:n =1.453,n =1.498,n =1.499, 2V _x =16°,Y=b,X c=11°. Kristallstruktur: RaumgruppeP2₁/a,a=26.560(3),b=15.256(2),c=6.505(1) Å, =92.90(1)°,Z=4;R=0.029 für 5126 unabhängige, mit MoK -Strahlung gemessene Reflexe. Die Struktur enthält isolierte Mg(H₂O)₆-Oktaeder, UO₂(CO₃)₃-Gruppen und freie Wassermoleküle, die ausschließlich durch Wasserstoffbrücken miteinander verknüpft sind.

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With 4 Figures     

Heavy-ion irradiation on crystallographically oriented cordierite and the conversion of molecular CO2 to CO: a Raman spectroscopic study

Crystallographically oriented sections of natural gemstone quality cordierite single-crystals have been irradiated with swift heavy ions of GeV energy and various fluences. Irradiation effects on the crystal lattice were investigated by means of Raman spectroscopy. Raman line scans along the trajectory of the ions reveal a close correlation of beam parameters (such as fluence and energy loss dE/dx along the ion path) to strain due to associated changes in lattice dimensions and defect concentration. The luminescence background also scales with the ion fluence and suggests the formation of point defects, which could also account for the macroscopically observable colouration of the irradiated samples. In addition, changes in the amount and nature of volatile species inside the structural channels are observed. They also scale with dE/dx and confirm the previously postulated irradiation-induced conversion of CO₂ to CO. Irradiations along the crystallographic a-, b- and c-axis reveal no significant anisotropy effect with respect to lattice alterations. The polarisation characteristics of the Raman-active modes confirm the preferred molecular alignment of CO and CO₂ along the a-axis direction.