Late Eocene to early Oligocene quantitative paleotemperature record: Evidence from continental halite fluid inclusions

Climate changes within Cenozoic extreme climate events such as the Paleocene–Eocene Thermal Maximum and the First Oligocene Glacial provide good opportunities to estimate the global climate trends in our present and future life. However, quantitative paleotemperatures data for Cenozoic climatic reconstruction are still lacking, hindering a better understanding of the past and future climate conditions. In this contribution, quantitative paleotemperatures were determined by fluid inclusion homogenization temperature (Th) data from continental halite of the first member of the Shahejie Formation (SF1; probably late Eocene to early Oligocene) in Bohai Bay Basin, North China. The primary textures of the SF1 halite typified by cumulate and chevron halite suggest halite deposited in a shallow saline water and halite Th can serve as an temperature proxy. In total, one-hundred-twenty-one Th data from primary and single-phase aqueous fluid inclusions with different depths were acquired by the cooling nucleation method. The results show that all Th range from 17.7°C to 50.7°C,with the maximum homogenization temperatures (ThMAX) of 50.5°C at the depth of 3028.04 m and 50.7°C at 3188.61 m, respectively. Both the ThMAX presented here are significantly higher than the highest temperature recorded in this region since 1954and agree with global temperature models for the year 2100 predicted by the Intergovernmental Panel on Climate Change.

aqueous fluid inclusions from halite in SF1 (probably late Eocene to early Oligocene). We used the cooling nucleation method to directly measure deposition temperatures of halite. This method has been proven to be very effective and has been widely used in reconstructing ancient climate from different geologic time periods, including Precambrian 19 , Permian 20,21 , Eocene 11 , Quaternary 22 , and modern 23 . In addition, a series of experiments 21,22,24,25 has demonstrated that the maximum homogenization temperature (Th MAX ) of halite fluid inclusions can represent the highest temperature of the water body in which the halite deposited and faithfully reflect the ancient climate. Thus, we chose Th MAX from all samples in SF1 as a record of paleotemperatures in the Shulu Sag during this time.
The Shulu Sag is located on the southern edge of the Jizhong Depression of the Bohai Bay Basin (North China), and surrounded by the Hengshui and Xinhe Faults on its northern and eastern margins, and the Ningjin and Xiaoniuchun uplifts along its western and southern margins (Fig. 1). It is a typical half graben-like fault basin 26,27 formed during the Eocene. Halite samples were collected from drill core in the southern Shulu Sag (Fig. 1) and preserved well since there were few volcanic thermal fluid events during the Paleogene to Neogene 28 .
The Shahejie Formation can be divided into four members (SF1, SF2, SF3, SF4) from bottom to top, based on petrologic characteristics (Table 1). The SF1 is late Eocene to early Oligocene in age and consistent with the First Oligocene Glacial (Oi-1) in time. During the deposition of SF1, the Shulu Sag was separated by two uplifts into three sub-sags from north to south. The sub-sag where the study borehole located was a typical continental saline lake with high salinity 29 .
The SF1 discussed in this study is characterized by evaporite sequences consisting of thin clastic layers shaped like bamboo kont (dark-gray mudstone or shale) and argillaceous limestone (Fig. 2). Halite in SF1 occurs in beds within which primary sedimentary structures or textures are well preserved (Figs. 3A and 3B). Chevron or cumulate crystals are widespread (Figs. 3C and 3D) and of which no deformation has been observation. All the evidences suggest that halite samples used in this paper are not altered and their Th values can be good climate proxies.

Results
Primary fluid inclusions in SF 1 halite occur in chevron-or cumulatetype crystals (Fig. 4). Chevron crystals typically form at the bottom of saline lakes with depths less than 60 cm 30 , so the Th of fluid inclusions in these crystals is analogous to ancient air temperatures 11,[21][22][23]25,31 . Cumulate crystals usually form at the air-water interface 20,21,23 and sink to the bottom under gravity. If cumulate crystals occur in the same beds with chevron crystals, the Th of the two types of fluid inclusions can be used to study ancient air temperatures 11,[19][20][21][22]31 . Chevron and cumulate crystals were found in both samples B493 and B1003, which indicates that the halite studied here was deposited in shallow water and the Th of fluid inclusions can be used to interpret paleoenvironmental conditions.
In total, about 360 pieces of halite from samples B493 and B1003 have been observed in detail and only 38 pieces of halite are available to Th analysis due to primary fluid inclusion in most of the halite pieces are few or absent. The Size of primary fluid inclusions (both of cumulate and chevron crystals) range from 2 to 20 mm and up to 40 to 50 mm. Primary fluid inclusions coexist in both single liquid and gas-liquid phases, and only the single-phase liquid fluid inclusions are chose for Th analysis. The Th of halite fluid inclusion was tested with the cooling nucleation method, and the results are shown in Table 2.
Sample B493: Sixty-one Th data of primary and single-phase aqueous fluid inclusions were obtained (

Discussion
Changes of Th values from the same sample or even the same inclusion band may be caused by seasonal or diurnal temperature fluctuations 20,23 . Consensus is that the Th MAX of single liquid phase  inclusions can represent the highest brine temperature both at the bottom and at the air-water interface 11,22,25 . The ranges of Th are different from chevron and cumulate crystals from sample B1003 because the number of fluid inclusions in chevron crystals is smaller than that in cumulate crystals. However, the range and average values of Th from these two types of halite crystals in sample B493 are very similar. The Th from both samples characterized by normal distribution, and co-occurrence of chevrons and cumulates in the same beds suggests the Th is valid and representative. The Th values indicate that the water temperature of ancient salt lakes ranged from 17.7 to 50.7uC, and ancient air temperatures had corresponding changes in this region.
As mentioned earlier, the Th MAX of single-phase, aqueous fluid inclusions represents the highest air temperature during halite deposition. The Th MAX in Shulu Sag during formation of SF1 is 50.7uC, which is 9.2uC higher than the highest temperature recorded since 1954 in this region (local temperature data, and Wu et al. 32 ). Given that the Th MAX of single-phase aqueous fluid inclusions in halite from modern salt lakes is slightly (less than 5uC) higher than the air temperature 33,34 , we infer that paleotemperatures during deposition of the SF1 were at least 4.2uC higher than the temperatures of the past 60 years. Because the study area has not significantly displaced over the last 65 Ma 13,14 and the Th MAX values of these two samples (sampling interval is about 160 m) are very similar, we speculate that the higher temperatures state evidenced by Th of halite fluid inclusion in the Shulu Sag may last a considerable time. Combining with the Eocene paleotemperature data from other places in China 11 , it implies that higher temperatures were widespread in eastern China during this interval. This phenomenon of higher temperature is well correlated with the occurrence of large-scale evaporite deposits in the same area during that time. In addition, the average temperature in China has risen by 0.5-0.8uC over the past 100 years 35 , while global temperatures are predicted to rise 1.4-5.8uC by 2100 11,36 . This study of homogenization temperatures of fluid inclusions from mid and late Eocene halite in Hubei, China, also indicates that paleotemperatures at the time were 4.6uC higher than today's temperatures 11 . Therefore, it can be predicted that climate warming will continue and not be reversed in the short term.

Methods
Halite samples were collected from two depths ( Fig. 2; 3028.04 m, sample number B493 and 3188.61 m, sample number B1003). Before determining the Th of fluid inclusions, halite samples were chosen by XRD (D/max-rA12kw, Rigaku Corporation, Japan). Temperature information is susceptible to distortion due to alteration of halite fluid inclusions by dissolution or heating during sawing. We referred to the methods outlined in Roberts and Spencer 23 , Lowenstein et al. 22 , Benison and Goldstein 20 and split the halite samples with a hammer and chisel along cleavage planes, into fragments with thicknesses of 0.5 to 1 mm. All the halite fragments were so smooth that changes to the fluid inclusions could be monitored under a microscope during heating and cooling. We observed and photographed these cleavage flakes under the microscope, and documented the occurrence and morphology of primary fluid inclusions. Halite samples were then sealed in self-sealing plastic bags and put into an airtight plastic box. Desiccant was added to the box for moisture protection, and the box was then transferred into a Haier freezer for about 1 week (multiple measurements showed that the temperature was stable at 218uC). After the single-phase fluid inclusions were frozen to nucleate bubbles (Fig. 6), we measured Th using a Linkam THMSG600 heating and cooling stage. The heating rate of the stage was first set at 0.5uC/min, but was lowered to 0.1-0.2uC/min when approaching 20uC.