1. Introduction
Pinnoite (MgB
2O
4∙3H
2O) is one of the ~20 naturally occurring Mg-borate minerals identified as of 1996, and it is one of the borates important in commercial deposits under the circumstance that only a comparative few of the 230 borates are that important [
1]. Notably, a pinnoite ore-layer found from the subbottom sedimentary sequence with a spatial distribution over ~10 km
2 in the central DaQaidam saline lake [
2,
3] is of great significance in gaining information for better understanding of the pinnoite-precipitating brine chemistry and constraints on pinnoite deposit formation.
DaQaidam Salt Lake is one of the three salt lakes containing solid-phase boron deposit among 25 salt lakes in Qaidam Basin, northwestern China. The borate ore bodies distributed in the eastern shore of the lake began to be used as a commercial product probably as early as in 970 AD [
4]. Geological and mineralogical study of the onshore borate deposit found that ulexite (NaCaB
5O
8∙8H
2O) and hydroboracite (CaMgB
6O
11∙6H
2O) are the dominant borate minerals, and that the input of boron-bearing water from hot springs from Mt. Dakendaban has been of great importance for the formation of Na–Ca- and Ca–Mg-borate deposits [
5,
6]. According to Qu et al. (1981), hydroboracite occurs as 0.5–2 mm spherical grains in the ore layers within gypsiferous deposits, and the borate ooids comprise ~70% hydroboracite in addition to dolomite or hydromagnesite and clay. Both primary and secondary ulexite minerals were identified from the onshore borate deposit. The former was primarily formed in the NaCl supersaturated brine with lower SO
42− and Mg
2+, but richer in Ca
2+. The latter occurred in the form of ulexite nodules capping on top of the hydroboracite layers, which were converted from hydroboracite [
5]. Subordinate borate minerals identified from the onshore deposit include kurnakovite (MgB
3O
3(OH)
5·5H
2O), pinnoite, inderite (MgB
3O
3(OH)
5·5H
2O), hungchaoite (MgB
4O
5(OH)
4·7H
2O), and carboborite (Ca
2Mg(CO
3)
2B
2(OH)
8·4H
2O). Experimental result indicates that hungchaoite is stable in the H
3BO
3 solution rich in Mg
2+, and it is transformed into inderite or kurnakovite when the solution is diluted or supplemented with borax. The onshore borate deposit is overall characterized by the site-to-site different occurrence of the borate minerals, indicating a complex deposition system in which geochemical conditions at one site differed from another in a very short distance [
5]. Interestingly, borate deposit found from the offshore evaporitic sequence (
Figure 1, dotted area in the saline lake) contains only pinnoite, which was formed on the paleo-lake bottom earlier than the onshore borate formation [
2,
3,
5,
7]. In order to better understand the sedimentary process and chemistry of the ore-forming brine associated with the genesis of the Mg-borate deposit, we have performed field investigations to examine the mode of occurrence of the pinnoite ore-layer in the subbottom evaporitic sequence and an integrated lithologic and mineralogical study of a type section, D3, selected from the center of the offshore borate deposit (
Figure 1). Based on the results from our field and laboratory investigations, we discuss hydroclimatic, geochemical and sedimentologic constraints on the pinnoite deposit formation in DaQaidam saline lake.
Study Area
DaQaidam Salt Lake comprises both saline lake and salt flat with a total area of about 235 km
2 (
Figure 1). It lies in a closed-drainage subbasin of the northern Qaidam Basin with a large catchment area of more than 2000 km
2. Geologically, the catchment area is situated in the tectonic belt between Qilian Block and Qaidam Block. Mt. Luliang to the southwest of the lake (
Figure 1) is an eclogite-bearing terrane, the part of the North Qaidam ultra-high pressure metamorphic (UHPM) belt [
8]. Mt. Dakendaban to the northeast contains probably the largest granite terrane in western China with an area of ~2200 km
2, which intruded into country rocks including medium- and high-grade Proterozoic metamorphic rocks, Paleozoic sedimentary, and intermediate-mafic volcanic rocks [
9]. According to Li [
10], the calculated boron Clarke value of the region is about nine times higher than the global mean value. Nevertheless, the inflow of hot spring waters from Mt. Dakendaban (
Figure 1;
Table 1 [
6]) played a key role in providing sufficient amounts of boron-bearing water for evaporative formation of borate deposits in DaQaidam Salt Lake.
DaQaidam saline lake shows Mg
2+–SO
42− type of hypersaline brine with total dissolved solid up to 375 g/L.
Table 2 [
12] shows ion concentrations and other parameters of the brine measured before mining the subbottom pinnoite deposit. The lake is fed by a number of streams originating mainly from the northeastern high altitude mountains. None of the streams are perennial. All ephemeral streams maximize their river-runoff in summer months when precipitation in the mountain catchment is enhanced. The enlargement of the saline lake occurs in summer months, inundating part of the salt flat. Some streams seep into underground in the piedmont of Mt. Dakendaban, continue their subsurface drainage within alluvial fans towards the terminal saline lake.
According to a monthly record from 1961 to 1962, the annual precipitation and evaporation at DaQaidam Salt Lake is respectively 33.3 mm and 2316.2 mm, and E/P ≈ 70. Under such an arid condition maintaining DaQaidam saline lake perennial requires inflow water supply from large amounts of precipitation-related stream runoff from mountain catchment. Changes in lake level and water chemistry could result from the changes of hydroclimatic conditions, which can be documented in the sediment record. In other words, a prominent shift in lithology may result from a marked change of the sedimentation regime associated with an abrupt hydroclimatic change [
13], and variations in the mineralogical composition of the evaporitic sediment are the consequence of chemical changes of the saline lake, linked with changes in inflow/evaporation. About 85% of the annual evaporation occurs in May–October [
14]. The contrasting rates of evaporation between summer and winter exert an important control on the chemical sedimentation of the saline lake. The contrasting rates could be amplified in the past warmer period, resulting in more intensified summer evaporation, which will be discussed later in the paper.
4. Discussion
One of the important facts revealed by this study is the ubiquitous distribution of the yellowish-gray clastic sediment, which functions as the major aquifuge confining the interstitial brine in the overlying evaporitic sequence (
Figure 1,
Figure 2 and
Figure 3). According to mining record, the pinnoite ore-layer as a basal evaporitic deposit occurred always on top of the yellowish clastic sediment. The pinnoite ore-layer may not occur everywhere over the mining area of the saline lake and the occurring depth and thickness of the pinnoite ore-layer may vary from site to site. This is attributable to the paleo-topography of the saline lake bottom before the evaporitic deposition. Field observation found that the visible sediment character, such as sedimentary structure, of the evaporitic deposit above the pinnoite ore-layer show differences among excavated sediment sections. For such a shallow saline lake, the past changes of lake level and water chemistry on seasonal/decadal/centennial time scales may have resulted in the lateral differences.
The pinnoite deposit was previously anticipated to be formed in the stage following carbonate deposition [
5]. We have however found solid evidence that the pinnoite ore-layer overlies right on clastic sediments (
Figure 2), and that the Mg-boron deposit marked the onset of the evaporitic deposition in the central area of the DaQaidam saline lake. The lithostratigraphic evidence clearly indicates a transition from clastic to Mg-borate deposition in the lacustrine environment. In fact, the sequential pattern from clastic directly to evaporitic deposition with no carbonate facies in between is not of surprise as it has occurred in other saline lakes in the arid Qaidam Basin as the consequence of abrupt hydroclimatic change [
16,
17]. Our investigation found that the hydrological response to climate warming in high altitude mountain catchments contrasts strikingly to that in the hyperarid Qaidam Basin: (1) precipitation is enhanced in high-altitude mountain catchments because warmer surface trigger condensation in mountainous topography by increased vertical airflows [
16], which increases catchment runoff draining into the terminal saline lakes in the basin where annual precipitation is around 30 mm and (2) aridification is intensified in the Qaidam Basin as the consequence of warming-induced enhancement of evaporation under the circumstance of a little increase of precipitation in the basin. As a result, the inflow water maximized in summer months is quickly enriched by the intensified evaporation, resulting in evaporite deposition. The sudden shift to evaporite formation induced by abrupt hydroclimatic change also explains why there occurred no carbonate sedimentation between clastic and evaporite deposition. A carbonate facies, if it occurred, would represent the gradual enrichment process of a deeper freshwater lake. In the case of DaQaidam saline lake, sediment evidence suggests a rather shallow lake environment during the deposition of the basal clastic sediment due to the limitation in both catchment inflow and summer evaporation under a cold glacial climate. Moreover, what is also important in regard to the deposition of the pinnoite ore-layer is the increased input of boron-bearing water supply from hot springs. The boron ion concentration of the hot spring water ranges between 39.8 and 49.5 mg/L, according to our recent measurements. The fact that the outflow of the hot springs peaks during the summer months confirms that the circulation of the underground hot water links with the seepage of the atmospheric precipitation. The increased inflow of boron-bearing water at the beginning of the evaporite deposition was associated with warming-induced enhancement of mountainous precipitation that brought about increased outflow from hot springs. Therefore, the differential effect of climate warming between high mountain catchment and the arid basin is crucial for the formation of evaporitic sequence and associated boron deposits in DaQaidam saline lake. Questions may arise as to why there is no pinnoite deposition today on the lake bottom of DaQaidam saline lake, where an eight-year average value of boron ion concentration was as high as 532 mg/L [
10].
Results suggest that geochemical and sedimentologic conditions most favorable for pinnoite deposit formation include: (1) more alkaline conditions than today with pH between 9 and 9.3, as evidenced by the co-deposition of large amounts of hydromagnesite; (2) sufficient amounts of Mg
2+ and boron ions in the ore-forming brine; and (3) a shallower to nearly desiccated paleo-lake, as implied by the cementation of the Mg-borate layer and by much smaller paleo-lake size as confined by the mining area (
Figure 1) of the pinnoite deposit. In addition, the Mg/Ca ratio is most likely an important factor affecting whether the brine favors pinnoite precipitation. In some modern lacustrine environment, hydromagnesite precipitation is associated with an extremely high Mg/Ca molar ratio >39 [
18]. By comparison, DaQaidam saline lake today has a pH 7.9, a Mg/Ca molar ratio 35.6, boron concentration of 532 mg/L, and a much enlarged lake size. As such, it is not surprising that pinnoite precipitation has ceased today in the offshore area of the saline lake, which is also confirmed by the data of XRD analysis for sediment trap collections. Neither have any borate minerals been detected, including pinnoite, from the evaporitic sediment deposited approximately in the last 1000 years in the middle of the DaQaidam saline lake [
19], simply because the geochemical and sedimentologic conditions since then became unfavorable for pinnoite precipitation.
The Miocene Kirka borate deposit, the world’s most important B
2O
3 producer, is one of the borate districts of the Neogene Basins in western Turkey. A horizon of Mg-borates discontinuously overlies the main orebody of borax in the central lacustrine basin, and the Mg-borates were attributed to be the ultimate evaporitic precipitates from the fractionation of the initial boratiferous brine, instead of previous interpretation as the products of reaction between preexisting borates and groundwater [
20]. The study of the borate deposit at Eagle Borax spring, Death Valley, California has recognized that magnesium is a significant component of borate-precipitating waters, from which the precipitation of borates and associated minerals at different concentration stages can be shown by a modified chemical divides diagram [
21]. According to Crowley [
21], depending on the initial Ca + Mg/HCO
3 + BO
3 ratio, waters evolve toward compositions either enriched in bicarbonate + borate and depleted in Ca + Mg or vice versa. In the study of the pinnoite deposit at DaQaidam, we found that a suitable alkalinity of the initial brine is indeed crucial for the formation of the Mg-borate deposit, in addition to the presence of sufficient amounts of B and Mg or, precisely, a very high Mg/Ca ratio, as discussed above in the paper. When the paleo-lake water maintained sufficient Mg
2+ with a pH buffered around 9.3, seasonal variations in lake-level and water chemistry, as a function of inflow/evaporation budget, determined which mineral(s) precipitate including pinnoite, hydromagnesite and halite at different time of a year. It is proposed that the fine pinnoite crystals in the subbottom ore-layer (
Figure 4a) precipitate during the summer months when evaporation has substantially enhanced following the enlargement of the saline lake by water inflows from the precipitation-induced runoff of the mountain catchment. We also propose a co-precipitation mode of both pinnoite and hydromagnesite basically formed as the consequence of evaporitic enrichment of the lake waters. It is however possible that the primary precipitation of pinnoite was ahead of hydromagnesite on seasonal scale of a year because of kinetic factors [
22], as noted by Crowley [
21].
The deposition of the pinnoite ore-layer ceased abruptly following the Mg-borate deposition for a century (estimated based on lamination counting), which gave way to the dominant precipitation of gypsum (
Figure 2a,c,d). Hydromagnesite, which was abundant and inversely covarying with pinnoite in the ore-layer, became absent in the overlaying gypsum layer (
Figure 2e). This changeover is attributed to: (1) decreased boron concentration of the water as a result of pinnoite precipitation and (2) decreased Mg and accumulatively increased Ca of the water due to hydromagnesite precipitation during the deposition of the ore-layer. Most likely, it reflects a dynamic shift of the water composition type from Mg > Ca/(HCO
3 + BO
3) > SO
4 to Mg < Ca/(HCO
3 + BO
3) < SO
4 on decadal to centennial scale in the depositional system of DaQaidam saline lake. Further investigation is required on the evaporite sequence and pinnoite ore-bodies of DaQaidam saline lake in order to add new information for the calculation of phase relations for Mg-borates and other evaporites.