The Formation of Li-salts from Natural Brines During Isothermal Evaporation at 25 ℃

Lithium and its compounds have very important applications in the new energy sources, new materials, and information technique industries. Lithium has two types of resources in nature: hard rock, e.g. Spodumene (LiAlSi2O6), Petalite(LiAlSi4O10), Lepidolite(K(Li,Al)3(Si,Al)4O10(F,OH)2), and brines, e.g. salt lake brines, oil well brines, underground brines etc. The biggest producer of Li commodities SQM in the world produces Li compounds from brines of famous salt lake Atacama on the central Andes Mountains in Chile     

Isothermal Evaporating Phase Equilibria in the Quaternary System (LiCl+NaCl+Li2SO4+Na2SO4+H2O)at 348.15 K and 0.1 MPa:An Experimental and Theoretical Study

The gradient solar pond technique is an economic separating process employed in the inorganic chemical industrial production of salt lake chemical engineering processes. In this paper,a novel isothermal evaporation experimental method was employed to simulate the evaporation phase equilibrium for the reciprocal quaternary system( LiCl + NaCl + Li_2 SO_4+ Na_2 SO_4+ H_2 O) at 348. 15 K to serve as a useful guide for lithium salt production via the depth solar ponds. The isothermal evaporation equilibrium solubilities and physicochemical properties,including the densities and pH values,were experimentally investigated. The dry-salt phase diagram,water-phase diagram,and the diagram of the physicochemical properties versus composition were plotted with respect to the experimental data. The drysalt phase diagram consists of three invariant points,seven univariant solubility curves,and five crystallization regions,specifically halite( NaCl,Ha),thenardite( Na_2 SO_4,Th),double salt( Li_2 SO_4·Na_2 SO_4,Db_2),lithium sulfate monohydrate( Li_2 SO_4·H_2 O,Ls),and lithium chloride monohydrate( LiCl·H_2 O,Lc). Based on Pitzer and its extended HMW model,the Pitzer single salt parameters,mixing ion interaction parameters,and thermodynamic stable equilibrium constants for the quaternary system at 348. 15 K were obtained. The calculated phase diagram and experimental isothermal phase diagram at 348. 15 K exhibited a great difference. Based on these results,the isothermal evaporation phase diagram can truly reflect the salt sedimentary in salt lakes and can be applied as a useful guide for the solar pond process.     

A Raman investigation on the boron form occurring in salt lake brine during evaporation

Boron resources are abundant in Da Qaidam salt lake of Qaidamu Basin. It has been given great attention for the polyborate species present in brine. In this study, the Raman spectroscopy was applied to investigate the existing-form of boron in brine during evaporation. The prepared solutions of MgO·2B2O3-H2O, MgO·2B2O3-MgCl2 -H2O, and MgO·2B2O3-MgSO4-H2O was also evaporated and recorded to study the influence of boron concentration, pH, and electrolytes on the borate speciation in brine. The mononborates of B(OH)3 and B(OH)4- were found to be the only forms present in the original salt lake brine. Brine evaporation promotes the formation of polyborate anions B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- and also disappearance of the B(OH)4- ion in brine with boron concentration of more than 11 g/L in B2O3. The pentaborate ion of B5O6(OH)4- was sensitive to the solution pH and found to be appeared under the pH value of 8.0. While the hexaborate ion of B6O7(OH)62- was observed more dependent on the electrolyte of magnesium chloride due to its special properties, such as promoting boron accumulation, lowering solution pH, and also the strong af?nity for water molecules, which is beneficial to the polymerization of borate ions in brine. The interaction mechanisms among polyborate anions during evaporation had also been proposed.     

A Raman Investigation on the Boron form Occurring in Salt Lake Brine during Evaporation

Boron resources are abundant in the Da Qaidam Salt Lake of the Qaidamu basin in China,which has generated significant attention due to the presence of polyborate species in brine from this lake. In this study,Raman spectroscopy was used to investigate the existing form of boron in brine during evaporation. MgO·2 B_2 O_3-H_2 O,MgO·2 B_2 O_3-MgCl_2-H_2 O,and MgO·2 B_2 O_3-MgSO_4~-H_2 O solutions were also studied to determine the influence of boron concentration,pH,and electrolytes on the borate speciation from brine. The mononborates B( OH)_3 and B( OH)_4~-were found to be the only forms present in natural salt lake brine. Brine evaporation promoted the formation of the polyborate anions B_3 O_3( OH)_4~-,B_5 O_6( OH)_4~-,and B_6 O_7( OH)_6~(2-)and also promoted the disappearance of the B( OH)_4~-ion from brine at boron concentrations of more than 11 g/L B_2 O_3. The pentaborate ion B_5 O_6( OH)_4~-was sensitive to the solution pH and appeared only at p H values less than 8. 0. Meanwhile,the hexaborate ion B_6 O_7( OH)_6~(2-)was observed to be more dependent on the electrolyte magnesium chloride due to its special properties,such as promoting boron accumulation,lowering solution pH,and also its strong affinity for water molecules,which were all beneficial for the polymerization of borate ions in brine. Interaction mechanisms between polyborate anions during evaporation are also proposed herein. ake; evaporation; polyborate species; interaction mechanism.     

Extraction of Lithium from Salt Lake Brine using N523-TBP Mixture System

In this work,problems encountered by tri-butyl phosphate( TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N,N-bi-( 2-ethylhexyl) acetamide( N523) during lithium extraction was investigated,and its disadvantages were analyzed in the view of practical application. An N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used separately. The optimal composition of this mixture extraction system was determined to be 20% N523-30% TBP-50% kerosene.The effects of brine acidity,Fe/Li molarity ratio,phase ratio and chloride ion concentration on lithium extraction efficiency were discussed. The operation conditions in single-stage extraction were optimized as brine acidity = 0. 05 mol/L,Fe/Li molarity ratio = 1. 3,and phase ratio = 2. The high concentration of chloride ions in brine was beneficial for the extraction of lithium. The structure of the extracted complex was proposed as( LiFeCl_4·n N523·m TBP)·( 2-n) N523·( 2-m) TBP( m + n = 2) by chemical analysis and slope-fitting methods. The extraction thermodynamic functions were calculated preliminarily,and the results suggested that the extraction process was an exothermic( ΔH 0) and spontaneous( ΔG 0) reaction,and the degree of disorder increased( ΔS 0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both the fundamental theory and practical application.     

藏南羊卓雍错流域水化学状况及其形成机制（英文）

The hydrochemistry of alpine lakes reflects water characteristic and its response to climatic change. Over 300 water samples had been collected from 52 sites of 5 lakes and 7 inflowing rivers in the Yamzhog Yumco Basin, South Tibet, during 2009–2014, basing which the hydrochemical regime and its mechanism were analyzed along with the adoption of hydrological investigations in 1979 and 1984 as well. Results revealed that the waters were hard with weak alkalinity for the Yamzhog Yumco Basin. Most of them were fresh, and the rest were slightly saline. The hydrochemical types of 5 lakes(i.e., Lake Yamzhog Yum Co, Puma Yum Co, Bajiu Co, Kongmu Co, and Chen Co) were SO_4~(2–)–HCO_3~––Mg~(2+)–Na~+, HCO_3~–– SO2–2+4–Mg~(2+)–Ca, SO_4~(2–)–Mg~(2+)–Na~+, SO_4~(2–)–HCO_3~––Ca~(2+), and SO_4~(2–)–Na~+–Mg~(2+)–Ca~(2+), respectively. As for rivers, HCO_3~– and SO_4~(2–) were the major anions, and Ca~(2+) was the dominant cation. Lake Yamzhog Yum Co, the largest lake in the basin, exhibited remarkable spatial variations in hydrochemistry at its surface but irregular changes with depth. The weathering of evaporates and carbonates, together with evaporation and crystallization, were the major mechanisms controlling the hydrochemistry of waters in the Yamzhog Yumco Basin. Global warming also had significant impacts on hydrochemical variations.     

Extraction of Lithium from Salt Lake Brine using N523-TBP Mixture System

In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The lithium extraction behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) was investigated, and its defect was analyzed in the view of practical application. The N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used severally. The composition of this mixture extraction system was determined as 20%N523-30%TBP-50% kerosene. The effects of brine acidity, Fe/Li molarity ratio, phase ratio and chloride ion concentration on lithium extraction efficiency were discussed respectively. The operation conditions in single stage extraction were optimized as brine acidity=0.05 mol/L, Fe/Li molarity ratio=1.3 and phase ratio=2. The high concentration of chloride ion in brine was benefit for extraction of lithium. The structure of extracted complex was proposed as (LiFeCl4·nN523·mTBP)·(2-n)N523·(2-m)TBP (m+n=2) by chemical analysis and slope fitting methods. The extraction thermodynamic functions were calculated preliminarily, and the results suggested that the extraction process was an exothermic (ΔH<0) and spontaneous (ΔG<0) reaction, and the degree of disorder increased (ΔS>0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both fundamental theory and practical application.     

CONCENTRATION CHARACTERISTICS OF SOLUBLE IMPURITIES IN THE SURFACE SNOW OF COLLINS ICE CAP, KING GEORGE ISLAND, ANTARCTICA

Measurements carried out for the upper 10m firn/ice obtained at the main dome of Collins Ice Cap, King George Island, Antarctica revealed the direct relation of soluble impurities of snow mass to the composition of atmosphere aerosols. It was indicated that sea salt source dominates the atmosphere aerosol around Collins Ice Cap. The simultaneous variation shown by the concentration profiles of Na~+, K~+, Mg~(2+), Ca~(2+), SO_4~(2-), CI~-, Br~- and very close EF values (≈1) suggested their common marine source and similar deposition process. Besides the possible surface contamination,NH_4~+varied uniformly along deeper part of the core in concentration, which could be considered as background value of ammonium. A satisfactory explanation for NO_3~- concentration profile has not reached at present.     

Microstructure of NiSO4 Solution:A Combined DFT and EXAFS Study

The microhydration structure of nickel sulfate aqueous solution has been determined via density functional theory( DFT) calculation and extended X-ray absorption fine structure( EXAFS) spectroscopy. The geometric optimization and energy calculation of nickel sulfate hydrated clusters of the molecular formula [NiSO_4( H_2 O)_n]~0( n = 1-12) were determined via DFT using the B3 LYP method. Several possible initial structures were considered for clusters of each size to locate the equilibrium geometry.Based on the DFT calculation,the favorable structure of Ni~(2+)includes the six-coordinated form of [NiSO_4( H_2 O)_n]~0 clusters. The results of hydration energy calculation suggest that the six-coordinated contact ion pair( CIP) is the stable configuration for small hydration clusters( n≤5),while the solventshared ion pair( SSIP) represents the favorable structure for medium hydration clusters( 6≤n≤10).The solvent is separated by x water molecules( xSIP,x ≥2 is the number of water molecule between Ni~(2+)and SO_4~(2-)) in larger hydration clusters( n≥11). The EXAFS analysis of the NiSO_4 aqueous solutions and NiSO_4·6 H_2 O solid established that Ni~(2+)was surrounded by six water molecules tightly forming an octahedral structure in the first hydration shell,and no CIP was found from 0. 70 mol/L to 2. 22 mol/L( near saturation). The Ni-O distance and coordinated number were 2. 040 ± 0. 020 ? and 6. 0 ± 1. 0,respectively. These results are consistent with the DFT calculations for [NiSO_4( H_2 O)_n]~0 clusters. DFT and EXAFS are powerful techniques that can be used to enhance the resolution of NiSO_4 solution microstructure.     

Extraction of Cesium and Rubidium with 4-tert-butyl-2- (α-methylbenzyl) phenol from Salt Lake Brine

This work shows the extraction of cesium( Cs~+) and rubidium( Rb~+) from salt lake brine containing potassium( K~+) and magnesium( Mg~(2+)). The results show that 4-tert-butyl-2-( α-methylbenzyl) phenol( t-BAMBP) diluted in sulfonated kerosene( SK) has an excellent extraction effect. Infrared spectroscopic studies indicate that polymerize to form the dimer in the t-BAMBP when Cs~+or Rb~+were extracted. The effects of K~+,Mg~(2+),t-BAMBP concentration,the volume ratio of organic phase to aqueous phase( O/A) and the alkalinity( pH) of aqueous phase were investigated.The K~+and Mg~(2+)should be eliminated through precipitating before the extraction and separation of Cs~+and Rb~+. The optimum extraction conditions of the experimental brine were as follows: 0. 8 mol/L t-BAMBP diluted in SK,pH≥13,a phase ratio of 1: 1,and an extraction contact time of 2 min at room temperature. The optimal extraction yields of Cs~+and Rb~+were as high as 100% and 85. 8%,in addition,8. 76% of K~+was co-extracted. Further work would increase the extraction yield and selectivity of Rb~+and realize the efficient separation of Cs~+and Rb~+from brine.     

青藏高原蒸发皿蒸发量时空变化特征及其成因的定量分析(英文)

Despite the observed increase in global temperature, observed pan evaporation in many regions has been decreasing over the past 50 years, which is known as the "pan evaporation paradox". The "pan evaporation paradox" also exists in the Tibetan Plateau, where pan evaporation has decreased by 3.06 mm a-2 (millimeter per annum). It is necessary to explain the mechanisms behind the observed decline in pan evaporation because the Tibetan Plateau strongly influences climatic and environmental changes in China, Asia and even in the Northern Hemisphere. In this paper, a derivation based approach has been used to quantitatively assess the contribution rate of climate factors to the observed pan evaporation trend across the Tibetan Plateau. The results showed that, provided the other factors remain constant, the increasing temperature should have led to a 2.73 mm a-2 increase in pan evaporation annually, while change in wind speed, vapor pressure and solar radiation should have led to a decrease in pan evaporation by 2.81 mm a-2, 1.96 mm a-2 and 1.11 mm a-2 respectively from 1970 to 2005. The combined effects of the four climate variables have resulted in a 3.15 mm a-2 decrease in pan evaporation, which is close to the observed pan evaporation trend with a relative error of 2.94%. A decrease in wind speed was the dominant factor for the decreasing pan evaporation, followed by an increasing vapor pressure and decreasing solar radiation, all of which offset the effect of increasing temperature across the Tibetan Plateau.     

利用高分辨率卫星影像分析工业城市的土地利用

The spatial differentiation of land use changes of Tuticorin is studied using high resolution LISS III satellite imagery and Maximum Likelihood algorithms. The classification accuracy of 95.2% was obtained. In this study,the land use of Tuticorin is classified as settlement,salt pan,agricultural land,wasteland,water bodies and shrubs. The settlement area is increased to 4.6 km2 during the year 2001 and 2006. The settlement area change is mainly driven by growth of industries and migration of people from peripheral villages. Shrub is increased to 3.63 km2 in the six year period. Water logging due to growth of shrubs in Tuticorin leads to several environmental and health hazard. This study warrants proper urban planning for Tuticorin for sustainable use of resource and environment.     

三江源地区气候变化及其对径流的驱动分析(英文)

Based on the precipitation and temperature data of the 12 meteorological stations in the "Three-River Headwaters" region and the observed runoff data of Zhimenda in the headwater sub-region of the Yangtze River, Tangnaihai in the headwater sub-region of the Yellow River and Changdu in the headwater sub-region of the Lancang River during the period 1965-2004, this paper analyses the trends of precipitation, temperature, runoff depth and carries out significance tests by means of Mann-Kendall-Sneyers sequential trend test. Makkink model is applied to calculate the potential evaporation. The runoff model driven by precipitation and potential evaporation is developed and the influence on runoff by climate change is simulated under different scenarios. Results show that during the period 1965-2004 the temperature of the "Three-River Headwaters" region is increasing, the runoff of the three hydrological stations is decreasing and both of them had abrupt changes in 1994, while no significant trend changes happen to the precipitation. The runoff model suggests that the precipitation has a positive effect on the runoff depth, while the potential evaporation plays a negative role. The influence of the potential evaporation on the runoff depth of the Lancang River is found to be the significant in the three rivers; and that of the Yellow River is the least. The result of the scenarios analysis indicates that although the precipitation and the potential evaporation have positive and negative effects on runoff relatively, fluctuated characteristics of individual effect on the runoff depth in specific situations are represented.     

区域气候变化对西藏扎布耶、当雄错、班戈湖变化的影响（英文）

The lake hydrological and meteorological data of the Tibetan Plateau are not rich. This research reports the observed climatic data and measured water levels of saline lakes from the local meteorological stations in the Zabuye salt lake, the Dangqiong Co salt lake and the Bankog Co salt lake in recent two decades. Combining with satellite remote sensing maps, we have analyzed the changes of the water level of these three lakes in recent years and discussed the origins of the changes induced by the meteorological factors. The results show that the annual mean temperature and the water level reflect a general ascending trend in these three lakes during the observation period. The rising rates of the annual mean temperature were 0.08℃/yr during 1991–2014 and 0.07℃/yr during 2004–2014, and of the water level, were 0.032 m/yr and 0.24 m/yr, respectively. Analysis of changes of the meteorological factors shows the main cause for the increase of lake water quantity are the reduced lake evaporation and the increased precipitation in the lake basins by the rise of average temperature. Seasonal variation of lake water level is powered largely by the supply of lake water types and the seasonal change of regional climate.     

黄河源区径流对气候变化的响应及未来趋势(英文)

This study examines the hydrological and meteorological data of the source region of the Yellow River from 1956 to 2010 and future climate scenarios from regional climate model (PRECIS) during 2010-2020. Through analyzing the flow variations and revealing the climate causes, it predicts the variation trend for future flows. It is found that the annual mean flow showed a decreasing trend in recent 50 years in the source region of the Yellow River with quasi-periods of 5a, 8a, 15a, 22a and 42a; the weakened South China Sea summer monsoon induced precipitation decrease, as well as evaporation increase and frozen soil degeneration in the scenario of global warming are the climate factors, which have caused flow decrease. Based on the regional climate model PRECIS prediction, the flows in the source region of the Yellow River are likely to decrease generally in the next 20 years.     

通过现代观测来检验湖面蒸发对中国干旱、半干旱区湖泊水位变化的影响(英文)

Qinghai Lake and Zhuye Lake, ~400 km apart, are located in the northwest margin of the Asian summer monsoon. Water of these two lakes mostly comes from the middle and eastern parts of the Qilian Mountains. Previous studies show that the Holocene climate changes of the two lakes implied from lake records are different. Whether lake evaporation plays a role in asynchronous Holocene climate changes is important to understand the lake records. In this paper, we used modern observations beside Qinghai Lake and Zhuye Lake to test the impact factors for lake evaporation. Pan evaporation near the two lakes is mainly related to relative humidity, temperature, vapor pressure and sunshine duration. But tem-perature has different impacts to lake evaporation of the two lakes, which can affect Holocene millennial-scale lake level changes. In addition, differences in relative humidity on the millen-nial-scale would be more significant, which also can contribute to asynchronous lake records.     

The concentration variation features of sea salt ions and non sea salt ions in a firn core recovered from Princess Elizabeth Land, East Antarctica

A 51.85 m firn core drilled in Princess Elizabeth Land, Antarctica, during the 1996-1997 Chinese First Antarctic Inland Expedition, has been measured for δ 18 O and major ions. Based on the high quality data of the seasonal variations of major ions, the firn core was dated with errors within ±3 years. The 51.85 m firn core record extends for 251 years (A. D. 1745-1996). The results of the glaciochemistry data of the firn core show that the mean concentrations of Cl -, Na + and Mg 2+ are similar to those reported from other coastal areas in East Antarctica. However, mean concentrations of Ca 2+ are much higher than those reported from other regions, this anomaly phenomenon may be related to the strong local terrestrial sources. It is found that the variations of three kinds of sea salt ions (Cl -, Na + and Mg 2+ ) in the past 150 years show very similarly rising trends, which may be the results the Southern Hemisphere warming in the past century.     

黄河银川平原段河岸摆动速率变化及其影响因素(英文)

It is important to examine the lateral shift rate variation of river banks in different periods. One of the challenges in this regard is how to obtain the shift rate of river banks, as gauging stations are deficient for the study of river reaches. The present study selected the Yinchuan Plain reach of the Yellow River with a length of 196 km as a case study, and searched each point of intersection of 153 cross-sections(interval between two adjacent cross-sections was 1.3 km) and river banks in 1975, 1990, 2010 and 2011, which were plotted according to remote sensing images in those years. Then the shift rates for the points of intersection during 1975–1990, 1990–2010 and 2010–2011 were calculated, as well as the average shift rates for different sections and different periods. The results show that the left bank of the river reach shifts mostly to the right, with the average shift rates being 36.5 m/a, 27.8 m/a and 61.5 m/a in the three periods, respectively. Contemporarily, the right bank shifts mostly to the right in the first period, while it shifts to the left in the second and third periods, with the average shift rates being 31.7 m/a, 23.1 m/a and 50.8 m/a in the three periods, respectively. The average shift rates for the left and right banks during the period 1975–2011 are 22.3 m/a and 14.8 m/a, respectively. The bank shift rates for sections A, B and C are different. The shift rate ratio of the left bank in the three sections is 1:7.6:4.6 for shift to the left and 1:1.7:3.8 for shift to the right, while that of the right bank is 1:1.8:1.2 for shift to the left and 1:5.6:17.7 for shift to the right during the period 1975–2011. Obviously, the average shift rate is the least in section A, while it is maximum in section B for shift to the left and in section C for shift to the right. The temporal variation of the shift rate is influenced by human activities, while the spatial variation is controlled by the local difference in bank materials.     

The first geodetic investigation at the summit of Dome A,Antarctica

Dome A is the highest ice feature in the Antarctica,up to now,little is known about surface topography at Dome A.The first Chinese ITASE expedition was carried out from Zhongshan station to Dome A during the 1996/1997 austral summer. During the 2004/2005 austral summer,the traverse was extended to the summit of Dome A which is 1228 km from Zhongshan Station by 21st Chinese National Antarctic Research Expedition (CHINARE).The real-time kinematic (RTK) GPS survey was carried out in the summit of Dome A during 2004/05 austral summer.The surface to- pography of Dome A was drawn up using the kinematic double-frequency GPS data covering an area of about 70 km~2.The accuracy of the kinematic survey is in the range of 0.20 m.Precise surface topography,bedrock morphology and internal laye- ring geometry are important for the future selection of the best site for deep drilling at Dome A.