The influence of metal cations on 13C-18O bonds in carbonates is still under debate. This paper used ab initio method to investigate this kind of influence of Mg2+, Fe2+ and Zn2+ cations on 13C-18O bonds in precipitat...The influence of metal cations on 13C-18O bonds in carbonates is still under debate. This paper used ab initio method to investigate this kind of influence of Mg2+, Fe2+ and Zn2+ cations on 13C-18O bonds in precipitated aragonite, calcite and dolomite. The polynomials of Δ47 and reduced partition function ratios (RPFRs) for 13/12C, 14/12C and 18/16O of these minerals were given within temperatures ranging from 260 to 1500 K. We found that these cations significantly decreased the Δ47 values at the level of 10-3 - 10-2 per mil, comparing with pure crystals;and that if the Δ47 values were used to reconstruct the temperatures Ts, the deviation of T was about 7.2°C for, for instance, zinc-enriched aragonite, as discussed in our paper. It was suggested that due to such influence, researchers would better use a proper thermometer according to the main impurity metal cations in carbonates. We also found that according to the probability theory, the theoretical value of the influence of phosphoric acid on Δ47 of CO2 degassed from different carbonates was zero.展开更多
The 13C-18O bonds in carbonates are potential single-phase geo-thermometers. However, their theoretical distributions (noted as Δ47s) in CO2 degassed from calcite and aragonite with phosphoric acid are unclear. Thus,...The 13C-18O bonds in carbonates are potential single-phase geo-thermometers. However, their theoretical distributions (noted as Δ47s) in CO2 degassed from calcite and aragonite with phosphoric acid are unclear. Thus, the isotope reactions of 13C-18O bonds on the growing surfaces of calcite (0001) and aragonite (001) planes were investigated using ab initio techniques. It was found that these reactions determined 13C-18O clumped isotope signatures in bulk calcite and aragonite minerals with novel Δ47 polynomials: and for temperatures ranging from 260 to 1500 K. These theoretical results were in good agreement with the experimental data. In addition, the influence of phosphoric acid on these polynomials was at the level of 0.01‰.展开更多
The correlation between the δ^13C and δ^13C-δ^18O in primary carbonates is affected by several factors such as hydrological balance, total CO2 concentrations, climatic condition and lake productivity. The influence...The correlation between the δ^13C and δ^13C-δ^18O in primary carbonates is affected by several factors such as hydrological balance, total CO2 concentrations, climatic condition and lake productivity. The influence of these factors on the δ^13C-δ^18O correlation may be different on different time scales. In this paper, two different-type lakes in southwestern China, Lake Erhai and Lake Chenghai, are selected to investigate the influence of climatic pattern on the δ^13C-δ^18O correlation and to evaluate the reliability of the δ^13C-δ^18O covariance as an indicator of hydrological closure. The results show that there exists good correlation between the δ^13C and δ^18O in Lake Erhai （overflowing open lake） and in Lake Chenghai （closed lake）. This suggests that the δ^13C-δ^18O covariance may be not an effective indicator of hydrological closure for lakes, especially on short time scales. On the one hand, a hydrologically open lake may display covariant δ^13C and δ^18O as a result of climatic influence. The particular alternate warm-dry and cold-wet climatic pattern in southwestern China may be the principal cause of the δ^13C-δ^18O covariance in Lake Erhai and Lake Chenghai. On the other hand, a hydrologically closed lake unnecessarily displays covariant trends between δ^13C and δ^18O because of the buffering effect of high CO2 concentration on the δ^13C shift in hyper-alkaline lakes. We should be prudent when we use the covariance between δ^13C and δ^18O to judge the hydrological closure of lake.展开更多
文摘The influence of metal cations on 13C-18O bonds in carbonates is still under debate. This paper used ab initio method to investigate this kind of influence of Mg2+, Fe2+ and Zn2+ cations on 13C-18O bonds in precipitated aragonite, calcite and dolomite. The polynomials of Δ47 and reduced partition function ratios (RPFRs) for 13/12C, 14/12C and 18/16O of these minerals were given within temperatures ranging from 260 to 1500 K. We found that these cations significantly decreased the Δ47 values at the level of 10-3 - 10-2 per mil, comparing with pure crystals;and that if the Δ47 values were used to reconstruct the temperatures Ts, the deviation of T was about 7.2°C for, for instance, zinc-enriched aragonite, as discussed in our paper. It was suggested that due to such influence, researchers would better use a proper thermometer according to the main impurity metal cations in carbonates. We also found that according to the probability theory, the theoretical value of the influence of phosphoric acid on Δ47 of CO2 degassed from different carbonates was zero.
文摘The 13C-18O bonds in carbonates are potential single-phase geo-thermometers. However, their theoretical distributions (noted as Δ47s) in CO2 degassed from calcite and aragonite with phosphoric acid are unclear. Thus, the isotope reactions of 13C-18O bonds on the growing surfaces of calcite (0001) and aragonite (001) planes were investigated using ab initio techniques. It was found that these reactions determined 13C-18O clumped isotope signatures in bulk calcite and aragonite minerals with novel Δ47 polynomials: and for temperatures ranging from 260 to 1500 K. These theoretical results were in good agreement with the experimental data. In addition, the influence of phosphoric acid on these polynomials was at the level of 0.01‰.
基金the National Natural Science Foundation of China（Grant No.40673068）the National Basic Research Program of China（Grant No.2006CB403201）。
文摘The correlation between the δ^13C and δ^13C-δ^18O in primary carbonates is affected by several factors such as hydrological balance, total CO2 concentrations, climatic condition and lake productivity. The influence of these factors on the δ^13C-δ^18O correlation may be different on different time scales. In this paper, two different-type lakes in southwestern China, Lake Erhai and Lake Chenghai, are selected to investigate the influence of climatic pattern on the δ^13C-δ^18O correlation and to evaluate the reliability of the δ^13C-δ^18O covariance as an indicator of hydrological closure. The results show that there exists good correlation between the δ^13C and δ^18O in Lake Erhai （overflowing open lake） and in Lake Chenghai （closed lake）. This suggests that the δ^13C-δ^18O covariance may be not an effective indicator of hydrological closure for lakes, especially on short time scales. On the one hand, a hydrologically open lake may display covariant δ^13C and δ^18O as a result of climatic influence. The particular alternate warm-dry and cold-wet climatic pattern in southwestern China may be the principal cause of the δ^13C-δ^18O covariance in Lake Erhai and Lake Chenghai. On the other hand, a hydrologically closed lake unnecessarily displays covariant trends between δ^13C and δ^18O because of the buffering effect of high CO2 concentration on the δ^13C shift in hyper-alkaline lakes. We should be prudent when we use the covariance between δ^13C and δ^18O to judge the hydrological closure of lake.
