CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from U.S. Provisional Patent Application No. 63/286,076, filed on December 5, 2021, which is incorporated by reference herein in its entirety.

BACKGROUND

[0002] Plant life depends on sunlight to give the plant the energy it needs to grow and produce seed or fruit. Through the process of photosynthesis, plants convert sunlight into energy, and this energy is used to promote vegetative growth and plant reproduction. Any plant nutrient or combination of nutrients that encourages the efficiency of the photosynthetic process may give an advantage in plant health and yield.

[0003] Chlorophyll is the green pigment present in all green plants and is responsible for the absorption of sunlight that contributes to photosynthesis. In the com plant, for example, several key nutrients are involved in the formation and production of chlorophyll. Nitrogen (particularly in the form of urea and ammonium nitrate) and other nutrients such as magnesium optimize the production of chlorophyll.

[0004] The availability of these nutrients to plants is a persistent problem.

[0005] While urea is water soluble, it precipitates or “salts out” at relatively high temperatures. For example, urea 46-0-0 can be used to make urea solutions up to 47.82% by weight, a grade of 22-0-0 nitrogen solution, which has a salt out temperature of 11 °C. Liquid fertilizer that sits in aboveground storage tanks through a cold winter can undergo stratification, salting out, or both. Stratification results in pockets of varying product concentrations within an aboveground storage tank. With cold temperatures, some liquid fertilizers will salt out, leaving a combination of salted product and liquid product. The salted product can clog sprayers, planters, and applicators. [0006] Moreover, contacting magnesium chloride with nitrogen-containing fertilizers, e.g., 10-34-0 (ammonium polyphosphate) and 12-0-0-26 (ammonium thiosulfate), typically causes precipitation. Thus far, nitrogen and magnesium have been successfully combined in very low nitrogen concentrations (e.g., NutriMag™ 5 N-0 P-0 K-5.5 Mg manufactured by Innovative Surface Solutions) and/or including less advantageous forms of nitrogen (e.g., ammonium and nitrate, such as in 32-0-0 liquid).

[0007] What is needed is a single fertilizer solution, comprising both high urea-based nitrogen concentration and chloride (CT) and magnesium (Mg ²⁺ ) ions, that can be stored and applied using conventional storage and application apparatuses as a liquid at relatively cold (0 °C and below) ambient temperatures. It would be particularly beneficial if such a fertilizer solution could serve as a base matrix for other nutrients (e.g., potassium or phosphorus) as well.

SUMMARY

[0008] In one aspect, a liquid composition for use as a fertilizer is provided, the liquid composition produced by the steps in the order: (1) providing an about 30% aqueous solution of magnesium chloride and heating the solution to a temperature of at least about 60 °C; (2) providing dry urea 46-0-0 and adding the dry urea 46-0-0 to the heated aqueous solution of magnesium chloride to form a solid-liquid mixture; (3) agitating the solid-liquid mixture to dissolve the dry urea 46-0-0 and form the liquid composition, wherein the liquid composition is characterized in that: (i) it remains in liquid form for more than 24 hours at a temperature of at less than 0 °C; (ii) it has a pH between 7 and 8; and (iii) it has a fertilizer ratio of about 23.5 N - 0 P - 0 K - 3.5 Mg. In one aspect, the fertilizer ratio is about 24N - OP - OK - OS - 4Mg - 10C1 - 0.35B. In one aspect, the 30% aqueous solution of magnesium chloride is provided in about 49% w/w, and the dry urea 46-0-0 is provided in about 51% w/w.

[0009] In another aspect, a method for preparing a liquid composition for use as a fertilizer is provided, the method comprising the steps in the order: (1) providing an about 30% aqueous solution of magnesium chloride and heating the solution to a temperature of at least about 60 °C; (2) providing dry urea 46-0-0 and adding the dry urea 46-0-0 to the heated aqueous solution of magnesium chloride to form a solid-liquid mixture; (3) agitating the solid-liquid mixture to dissolve the dry urea 46-0-0 and form the liquid composition, wherein the liquid composition is characterized in that: (i) it remains in liquid form for more than 24 hours at a temperature of at less than 0 °C; (ii) it has a pH between 7 and 8; and (iii) it has a fertilizer ratio of about 23.5 N - 0 P - 0 K - 3.5 Mg. In one aspect, the fertilizer ratio is about 24N - OP - OK - OS - 4Mg - 10C1 - 0.35B. In one aspect, the 30% aqueous solution of magnesium chloride is provided in about 49% w/w, and the dry urea 46-0-0 is provided in about 51% w/w.

BRIEF DESCRIPTION OF THE FIGURES

[0010] FIG. 1 is a flow chart showing the steps of the method that lead to the claimed liquid fertilizer compositions comprising a complex of magnesium chloride and urea with mild hydration.

[0011] FIG. 2 is an example plant set-up for carrying out the steps of the method that lead to the claimed liquid fertilizer compositions.

[0012] Figure 3 shows the FTIR spectrum of urea.

[0013] Figure 4 shows the TGA profile for urea.

[0014] Figure 5 shows the FTIR spectra of MgCh*XH2O and MgC12*2H2O.

[0015] Figures 6A and 6B show the TGA spectra of MgC12*XH2O and MgC12*2H2O.

[0016] Figure 7 shows the FTIR spectra of: (i) an example claimed complex of magnesium chloride and urea with mild hydration (“N-Mag”); (ii) N-Mag crystallized at 40 °C; and (iii) N-Mag crystallized at 60 °C.

[0017] Figures 8A and 8B show the TGA spectra of N-Mag and N-Mag crystallized at 60 °C.

[0018] Figure 9 shows mass data for several molecular formulae. [0019] Figure 10 shows the FTIR spectra of N-Mag compared to two simple solutions of MgCh and urea.

[0020] Figure 11 shows TGA spectra of N-Mag compared to two simple solutions of MgCh and urea, in solution.

[0021] Figure 12 shows TGA spectra of crystals formed from N-Mag compared to crystals formed from two simple solutions of MgCb and urea.

DETAILED DESCRIPTION

[0022] In one aspect, a liquid composition for use as a fertilizer is provided, the liquid composition produced by the steps in the order: (1) providing an about 30% aqueous solution of magnesium chloride and heating the solution to a temperature of at least about 60 °C; (2) providing dry urea 46-0-0 and adding the dry urea 46-0-0 to the heated aqueous solution of magnesium chloride to form a solid-liquid mixture; (3) agitating the solid-liquid mixture to dissolve the dry urea 46-0-0 and form the liquid composition, wherein the liquid composition is characterized in that: (i) it remains in liquid form for more than 24 hours at a temperature of at less than 0 °C; (ii) it has a pH between 7 and 8; and (iii) it has a fertilizer ratio of about 23.5 N - 0 P - 0 K - 3.5 Mg. In one aspect, the fertilizer ratio is about 24N - OP - OK - OS - 4Mg - 10C1 - 0.35B. In one aspect, the 30% aqueous solution of magnesium chloride is provided in about 49% w/w, and the dry urea 46-0-0 is provided in about 51% w/w.

[0023] In another aspect, a method for preparing a liquid composition for use as a fertilizer is provided, the method comprising the steps in the order: (1) providing an about 30% aqueous solution of magnesium chloride and heating the solution to a temperature of at least about 60 °C; (2) providing dry urea 46-0-0 and adding the dry urea 46-0-0 to the heated aqueous solution of magnesium chloride to form a solid-liquid mixture; (3) agitating the solid-liquid mixture to dissolve the dry urea 46-0-0 and form the liquid composition, wherein the liquid composition is characterized in that: (i) it remains in liquid form for more than 24 hours at a temperature of at less than 0 °C; (ii) it has a pH between 7 and 8; and (iii) it has a fertilizer ratio of about 23.5 N - 0 P - 0 K - 3.5 Mg. In one aspect, the fertilizer ratio is about 24N - OP - OK - OS - 4Mg - 10C1 - 0.35B. In one aspect, the 30% aqueous solution of magnesium chloride is provided in about 49% w/w, and the dry urea 46-0-0 is provided in about 51% w/w.

[0024] In one aspect, the product is not simply a mixture or super-saturated mixture of the two starting products. Rather, the liquid composition comprises a complex of MgCL and urea (U) with mild hydration. In one aspect, the structure comprises MgChU^XHiO, wherein X = 1 to 6.

[0025] Urea, also known as carbamide, is an organic compound having the chemical formula CO(NH2)2. Urea 46-0-0, or urea 46% nitrogen, is a white crystalline solid containing 46% nitrogen. Urea 46-0-0 is widely used in the agriculture industry as a fertilizer. The designation “46-0-0” refers to a fertilizer ratio, in this case, an NPK (nitrogen-phosphorus- potassium) fertilizer ratio of 46 N:0 P:0 K. “Fertilizer ratio” means the ratio of two or more nutrients to another in 100 pounds of either liquid or dry material.

[0026] Urea is readily commercially available or may be manufactured by feeding ammonia and carbon dioxide into a reactor at 180 - 210 °C and 150 bar pressure. After stripping the reaction mixture of ammonia, the urea solution is concentrated by evaporation or crystallization.

[0027] MgCL is also commercially available, typically in the form of MgCh*6H2O crystals. Water is added to the crystals to achieve a desired concentration. For example, for a 30% MgCL solution, 14.88 lbs of MgCh*6H2O are mixed per gallon of water.

EXAMPLES

Example 1 : Preparation and characterization of MgChU XH O

[0028] With reference to FIGs. 1 and 2, a 30% MgCL solution (Compass Minerals) sourced from the Great Salt Lake in Utah is placed into a commercial fertilizer blender and heated to about 60 °C. Granular urea 46-0-0 (CF Industries) (51% urea to 49% MgCb w/w) is added slowly to the heated MgCb solution by hopper with forceful agitation. After the mixture becomes a homogeneous, slightly viscous, light brown liquid free of foreign matter, agitation is ceased, and the liquid is cooled and prepared for transport. The liquid product has a fertilizer ratio of about 23.5 N - 0 P - 0 K - 3.5 Mg, or about 24N - OP - OK - OS - 4Mg - 10C1 - 0.35B, a pH of about 7.5-7.8, and remains in liquid form below 0 °C for sustained periods.

[0029] The product (“N-Mag” or “NitroMag”) was evaluated by:

[0030] Fourier Transform Infrared (FTIR) Spectroscopy

Bruker Tensor II

MIRacleATR sampling accessory

4 cm' ¹ resolution, 16 scans per spectrum, 4000-600 cm' ¹

[0031] Thermogravimetric Analysis (TGA)

TA Instruments, Hi-Res TGA 2950 Thermogravimetric Analyzer

30 °C/minute ramp to 800 °C

Oxygen atmosphere

[0032] Figure 3 shows the FTIR spectrum of urea. Figure 4 shows the TGA profile for urea. Figure 5 shows the FTIR spectra of MgC12*XH2O and MgC12*2H2O. Figures 6A and 6B show the TGA spectra of MgC12*XH2O and MgC12*2H2O.

[0033] Figure 7 shows the FTIR spectra of: (i) N-Mag; (ii) N-Mag crystallized at 40 °C; and (iii) N-Mag crystallized at 60 °C. N-Mag is a combination of MgCb and urea with features of both represented in the FTIR spectrum. As the product is dried and crystallized, there is a slight decrease in absorbance in the 3000-3600 cm' ¹ region, indicating that the final product is mildly hydrated (in contrast to the MgCh’XHiO starting product that shows more dramatic changes in this region as the product is dried). [0034] Figures 8A and 8B show the TGA spectra of N-Mag and N-Mag crystallized at 60 °C. TGA of N-Mag does not show clear transitions that can be correlated to fragmentation of the molecule. TGA of the dried sample, however, shows two transitions. Because the weight change does not begin until the temperature reaches almost 200 °C, the initial weight loss is not attributed to water. If, instead, the mass loss of 72% is attributed to urea, a complex of MgChL would correlate to these data.

[0035] Figure 9 shows mass data for several molecular formulae. In TGA, molecules rarely break down to the bare metal atom, Mg in this case. The residue is generally an oxide, like MgO, or salt, like MgCh. Therefore, the mass percent of Mg or Cl alone is unlikely to correlate to the final stages of TGA.

[0036] N-Mag was next compared to simple mixtures of starting materials. First, MgCb (49% w/w) and urea (51% w/w) were combined at room temperature and mixed thoroughly until homogeneous. Second, MgCh heated to 60 °C prior to the addition of urea.

[0037] Figure 10 shows the FTIR spectra of N-Mag compared to the two simple solutions. FTIR spectra of the simple MgCh-urea solutions are very similar (the small baseline shift is not significant). When overlaid with the spectrum of the N-Mag product, there is a distinctive absorbance around 1100 cm' ¹ that is not present in the simple mixtures. This unique spectral feature supports that the N-Mag is a new complex, not simply a mixture of the starting materials.

[0038] Figure 11 shows TGA spectra of N-Mag compared to the two simple solutions, in solution. TGA profiles of the simple solutions and N-Mag are similar until temperatures exceed 550 °C. Above 550 °C, there is a distinctive shift in the profile for N-Mag. This shift supports that the N-Mag is a new complex, not simply a mixture of the starting materials.

[0039] Figure 12 shows TGA spectra of crystals formed from N-Mag compared to the two simple solutions. Crystals formed from the simple mixtures produced very similar TGA profiles. There is a distinctive shift in the profile for the N-Mag throughout the temperature ramp. This shift further supports that the N-Mag crystals represent a new complex, not cocrystallization of the starting materials.

Example 2: Fertility Test (Plot Scale)

[0040] The liquid composition from Example 1 was compared to other formulations and tested on corn as follows:

Table 1: Formulations

Table 2: Application Method Table 3: Plot* Results

*Plot size: 4 rows, 47.5 ft/per row, 30” between rows

[0041] As shown in Table 3, the liquid fertilizer according to Example 1 (Formulation Nos. 5 and 7) resulted in consistent, significant increases over urea alone (20%) and the other nitrogen-containing blends (7-15%).

Example 3: Fertility Test (Field Scale)

[0042] Formulation No. 5 (NitroMag) was tested on #2 yellow corn. Each test was evaluated for yield results, plant health, stock quality, and nutrient uptake. Four test sites were evaluated during different com plant growth stages.

[0043] Trial #1 : The first trial with NitroMag was side dressed (fertilizer put in the ground by the root) on com at the V5 leaf stage. The comparison was done against regular 32% nitrogen. The test fields were visited weekly throughout the summer to observe the different stages of growth and how they compared to one another. The roots were healthy and well established. The ears on the NitroMag and 32% nitrogen-treated corn both filled all the way to the end and had similar girth and length. Toward the end of summer, NitroMag-treated plants were a darker color of green compared to the 32% nitrogen-treated plants. The darker green indicates that the NitroMag plant was healthier. For plant health, healthy chlorophyll molecules mean healthier corn leaves and more productive photosynthesis, which results in better stock health, nutrient uptake, and higher yields. The yield results validated the visual inspections: on an equal nitrogen basis, NitroMag had a five bushel/acre advantage over the 32% nitrogen.

[0044] Trial #2: The NitroMag was applied through Y-Drop (product sprayed on the ground, right beside where the com plant emerges from the ground) on corn at the V8 stage. The plants had a very strong green color. On an equal nitrogen basis, NitroMag had a 4.5 bushel/acre advantage over the 32% nitrogen.

[0045] Trial #3: The NitroMag was applied by fertigation (fertilizer was applied through irrigation pivots during watering) over two applications, pre-tassel and postpollination. The plant and stock health were consistent throughout the season. This trial was a comparison between 28-0-0-5 and NitroMag. The products were applied at the exact same time with the same amount of nitrogen. Both sides of the field were equally healthy and the ears on both sides had very comparable length and girth. The NitroMag yielded nine bushels/acre more than the 28-0-0-5. Stock quality was monitored throughout the trial, and the NitroMag had a very health pith (inside of the com stalk), while the 28-0-05 showed signs of stock rot.

[0046] Trial #4: This trial between NitroMag and ammonia was delayed due to rain and should have been applied sooner, which could have provided higher yields. The NitroMag was applied once by fertigation at brown silk, and the plant and stock health were very good. NitroMag showed a four bushel/acre yield increase.

Example 4: Stability Tests

[0047] The liquid composition from Example 1 was compared to other formulations and tested for temperature resistance:

Example 5: N-Mag as Base Matrix #1; N-Mag Plus Potassium (NK-Mag)

[0048] The addition of potassium to N-Mag improves N-Mag’ s efficiency for late season pivot applications and for use on other crops that require more potassium. The base matrix is N-Mag, which is blended back with dry soluble potash (0-0-60) ((i.e., put back in the blender and remixed with water and soluble potash in the correct amounts) as a re-blended mix to formulate a 19N-0P-3K-0S-3Mg-7Cl-0.25 B liquid product.

[0049] The same blend can be manufactured at the time the N-Mag is being made, by adding the correct amount of soluble potash to the other products used to formulate N-Mag liquid.

[0050] For back blending of N-Mag with soluble potash, the formula is: 80% NitroMag + 15-20% H2O + 5.3% Soluble Potash (0-0-60)

[0051] The amount of water may have to be increased if temperatures are colder. For example, at 20 lbs of water, potassium settles out of the mix. In warmer temperatures, 15 lbs will float the potassium.

[0052] A ton of NK-Mag product includes:

Nitro-Mag 80# x 20 = 1600 lbs

Water @ 15# x 20 = 300 lbs

Potash @ 5.3# x 20 = 106 lbs

Total amount = 2006 lbs

[0053] Making the NK-Mag product with this method permits existing N-Mag to be taken out of storage and blended in a timely fashion for delivery to, e.g., a farm, avoiding long term storage of the product. If long term storage is required, the water may be increased to 400 lbs in a ton batch. The NK-Mag can be cold blended with the proper agitation and adding the water first. [0054] For blending NK-Mag from scratch:

Nutri-Boost added at desired level

Magnesium Chloride 39% or 19,500 lbs in a 50,000 lb load.

Urea (46-0-0) 41% or 20,500 lbs in 50,000 lbs

Water at 15% or 7500# in 50,000 lbs

Soluble Potash (0-0-60) 5.3% or 2,650 lbs in 50,000 lb

[0055] Mixing instructions:

Nutri-Boost liquid stabilizer is added to the reactor first at the desired amount (e.g., 600 lbs).

Place 19,500 pounds of MgCb in the reactor to heat to 60-70 °C.

Place 7,500 lbs of H2O to the blend, continuing to heat and agitate.

Once the correct temperatures have been achieved, add 20,500 lbs of dry urea (46-0-0) to the mix while agitating.

[0056] As the mixture blends and a heat of at least 110 °F is maintained, add in the 2,650 lbs of dry soluble potassium (0-0-60). Continue to agitate until product is blended.

[0057] These instructions produce a 19 N-0 P-3 K-0 S -3Mg-7Cl-0.25B mix of NK- Mag. The NK-Mag product weighs 10.9 pounds per gallon.

Example 6: N-Mag as base matrix #2; various blends as corn starters or liquid phosphate category of products

[0058] Other than liquid nitrogen 32% and side dressing products such as 28-0-0-5 S, the highest usage of liquid fertility products is in the corn starter or liquid phosphate category of products. The most widely used phosphate product is a polyphosphate known as 10-34-0. In 100 pounds of product, 10-34-0 contains ten pounds of nitrogen and 34 pounds of phosphate. 10-34-0 is made by reacting a 68% phosphoric acid with anhydrous ammonia in an exothermic reaction. [0059] Unfortunately, the combination of MgCh with 10-34-0 product precipitates, resulting in clogged hoses and solids that must be removed from the bottom of large tanks.

[0060] Surprisingly, however, a stable phosphate source (e.g., 54% Merchant Grade Acid) and Nitro-Mag mix suitably with MgCb. Three such blends were prepared: [0061] 10-30-0

[0062] For a 10-30-0 blend, pump in the desired amount of 54% Merchant Grade Phosphoric Acid into a tank or tanker transport in a 55% ratio of the final gallon quantity needed. If blending a 4,500 gallon batch, 55% of those 4,500 gallons would be the phosphoric acid, or 2,475 gallons.

[0063] The next step is to back blend in the Nitro-Mag liquid by pumping it into the tank or tanker to freely mix with the 54% Phosphoric Acid. In this case, that would be 2,025 gallons or 45% of the blend with the Nitro-Mag liquid fertilizer.

[0064] The end result is a 10N-30P-0K-0S-3Mg-5Cl +Boron product.

[0065] 20-10-0 blend

[0066] For the 20-10-0 blend, the same procedure is followed, except that the ratios of the two reagents will change due to the different amounts of nutrients desired. To make a 4,500 gallon batch, first introduce the 54% Phosphoric Acid by pumping 18% of the phosphoric acid or 810 gallons into the tank.

[0067] The next step is to back blend in the Nitro-Mag liquid at 82% of the 4,500 gallons, or 3,690 gallons.

[0068] The end result is a 20N-10P-0K-0S-4Mg-7Cl +Boron product.

[0069] 17-15-0 blend

[0070] For the 17-15-0 blend, the same procedure may be used. Start by taking 28% of the 54% Phosphoric Acid or 1,260 gallons of a 4,500 gallon batch and pumping it into the tank. [0071] The next step is to back blend 72% or 3,240 gallons of Nitro-Mag into the same tank, letting it blend freely.

[0072] The end result is a 17N-15P-0K-0S-3.5Mg-6Cl +Boron product.

[0073] The success of these blends is based on the ability of 54% Merchant Grade Phosphoric Acid to blend well with MgCh in the presence of the Nitro-Mag base matrix.

Example 7: N-Mag as base matrix #3; various blends as corn starters or liquid phosphate category of products

[0074] To make a ton of 20N-12P-0K-0S-3.2Mg-9Cl-0.29B configuration:

(1) Add 1,680# of Nitro-Mag in the reactor while agitating.

(2) Add in 320# of a 75% Phosphoric Green Acid and continue to blend until well mixed.

[0075] To make a ton of 10N-28P-0K-0S-l.7Mg-4.6Cl-0.15B configuration:

(1) Add 840# of Nitro-Mag into the reactor with agitation and heat.

(2) Add 740# of 75% Phosphoric Green Acid and continue to agitate and heat.

(3) Add 420# water to the mix and continue to blend until well mixed.

(4) Heating temperatures on this blend should be at 38 °C.

Example 8: N-Mag as base matrix #4; various blends as corn starters or liquid phosphate category of products

[0076] To make a ton of 20N-12P-0K-0S-3.2Mg-9Cl-0.29B:

(1) Add Nutri -Boost Stabilizer at 25# or more to the reactor.

(2) Add 811# of MgCb into the reactor while mixing and heating.

(3) Add 320# of 75% Phosphoric Acid while mixing and heating to 60-70 (4) Add 844# of Urea to melt while continuing to mix until all solids are blended.

(5) If final product has unsuitably thick viscosity, up to 300# of water may be added per ton.

[0077] To blend a ton of 10-28-0K-0S-l.6Mg-4.6Cl-0.15B

(1) Add 25# or more of Nutri -Boost Stabilizer to the reactor.

(2) Add 400# of MgCh into the reactor while mixing and heating the product.

(3) Add 740# of 75% Phosphoric Acid while mixing and heating to 60-70 °C.

(4) Add 420# of water while mixing and heating.

(5) Add 415# of urea to melt while continuing to mix until all solids are blended.

[0078] The aspects disclosed herein are not intended to be exhaustive or to be limiting. A skilled artisan would acknowledge that other aspects or modifications to instant aspects can be made without departing from the spirit or scope of the invention. The aspects of the present disclosure, as generally described herein and illustrated in the figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are contemplated herein.

[0079] Unless otherwise specified, “a,” “an,” “the,” “one or more of,” and “at least one” are used interchangeably. The singular forms “a”, “an,” and “the” are inclusive of their plural forms. The recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). The terms “comprising” and “including” are intended to be equivalent and open-ended. The phrase “consisting essentially of’ means that the composition or method may include additional ingredients and/or steps, but only if the additional ingredients and/or steps do not materially alter the basic and novel characteristics of the claimed composition or method. The phrase “selected from the group consisting of’ is meant to include mixtures of the listed group.

[0080] When reference is made to the term “each,” it is not meant to mean “each and every, without exception.”

[0081] The term “about” in conjunction with a number is simply shorthand and is intended to include ±10% of the number. This is true whether “about” is modifying a standalone number or modifying a number at either or both ends of a range of numbers. In other words, “about 10” means from 9 to 11. Likewise, “about 10 to about 20” contemplates 9 to 22 and 11 to 18. In the absence of the term “about,” the exact number is intended. In other words,

“10” means 10.