# Patent

## Title
Optimized alumina coagulants for water treatment

## Abstract

Substitution of a single Ga-atom or single Ge-atom (GaAl12 and GeAl12 respectively) into the center of an aluminum Keggin polycation (Al13) produces an optimal water-treatment product for neutralization and coagulation of anionic contaminants in water. GaAl12 consistently shows  ̃1 order of magnitude increase in pathogen reduction, compared to Al13. At a concentration of 2 ppm, GaAl12 performs equivalently to 40 ppm alum, removing  ̃90% of the dissolved organic material. The substituted GaAl12 product also offers extended shelf-life and consistent performance. We also synthesized a related polyaluminum chloride compound made of pre-hydrolyzed dissolved alumina clusters of [GaO4Al12(OH)24(H2O)12]7+.

## Background
FEDERALLY SPONSORED RESEARCH
The United States Government has rights in this invention pursuant to Department of Energy Contract No. DE-AC04-94AL85000 with Sandia Corporation.


CROSS-REFERENCE TO RELATED APPLICATIONS
None
BACKGROUND OF THE INVENTION
Diminishing clean water supplies, due to increasing population and pollution, coupled with more stringent government regulations, require more effective materials for water treatment technologies. A global water crisis has forced us to redefine potable water resources to include challenged supplies, such as surface, brackish, produced and recycled waste water. Front-end water treatment technologies, coagulation in particular, should ideally remove the majority of organic, inorganic and microbiological contaminants to both ensure a consistent product and avoid the downstream treatment problems of disinfection byproducts and inorganic- or bio-fouling of filtration media.
Commercial coagulants for water treatment are usually some form of an iron or aluminum salt. If the pH is high enough, or by adjusting the pH (generally 7-8), a metal oxide/hydroxide precipitate/coagulant/floc forms that brings down water contaminants such as clay and organic matter. It is designed as a clarification process; but certain coagulant formulations are also effective in removing microbiological contaminants or pathogens. These can include viruses, bacteria and protozoa such as cryptosporidium.
The most commonly employed inorganic coagulants are ferric chloride and aluminum sulfate (alum). However, prehydrolyzed aluminum (or PACl—polyaluminum chloride) has consistently shown enhanced removal of a variety of contaminants, including natural organic matter (NOM), bacteriophage as model viruses, and turbidity (clays). Removal of Cryptosporidium via PACl/prehydrolyzed aluminum has given mixed results, when compared to the performance of alum or ferric. Additional commonly-known advantages of PACl over alum in particular include a wider optimal effective pH range, minimal pH change of the treated water, less temperature dependence, and smaller required dose-rate for equivalent or better water clarification. Disadvantages of PACl included the higher cost (but perhaps offset by lower dose rates) and reduced shelf-life.
The efficacy of PACl is attributed to soluble polycationic species that form upon base-hydrolysis of aqueous aluminum salt solutions. The most abundant polycationic specie is the ε-Keggin ion, [Al13O4(OH)24(H2O)12]7+(Al13). The widely accepted mechanism of contaminant removal is by charge-neutralization of anionic species, including clay particles, natural organic matter, viruses, bacteria, and spores. A better understanding of the efficacy of the Al13 Keggin ion in the contaminant removal process has lead to an optimization of aluminum coagulants. Issues that we considered include: 1) How does acid-base chemistry of aqueous Al13 affect its ionic charge in typical raw water media? 2) Is the alumina that precipitates from PACl the same as that which precipitates from alum during the coagulation process? 3) What is the source of PACl instability and how can this issue be dealt with?
To probe these questions, we have compared the aqueous behavior and contaminant removal efficacy of Al13 to its related Ga- and Ge-centered analogues ([GaAl12O4(OH)24(H2O)12]7+=GaAl12; [GeAl12O4(OH)24(H2O)12]8+=GeAl12). The ε-Keggin ion is illustrated in FIG. 1. Structurally, Al13, GaAl12 and GeAl12 are nearly identical. However, the rate of ligand exchange of water and hydroxyl ligands and the acidity of the bound-water protons vary significantly as a function of composition trending: GaAl12<Al13<GeAl12 and cluster stability to ligand exchange is GaAl12>Al13>GeAl12. Thus, while GeAl12 provides an isostructural polycation with a charge even higher than Al13, the relatively stable/inert GaAl12 affords the opportunity to investigate the issue of shelf-life of Al13-containing PACl. Since the central metal (Ga or Ge) of the Keggin ion is completely shielded by the twelve alumina octahedral, but significantly influences the molecules' aqueous chemistry, this work presents the perfect opportunity to probe and ultimately improve the mechanism of Al13 efficacy in water purification.
We performed a series of contaminant removal tests utilizing solutions of GaAl12, Al13, or GeAl12 added to raw river water from the Rio Grande in Albuquerque, N. Mex. Control studies using either alum or ferric were done in parallel, and we compared the removal of bacteriophage, dissolved organic carbon, Cryptosporidium, and turbidity using these coagulants and coagulant analogues. Electrospray Ionization Mass Spectrometry (ESI MS) measurements of aqueous solutions of GaAl12, Al13, or GeAl12 provided information on the aqueous forms of these species, while 27Al and 71Ga solid-state Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) revealed the state of the precipitated flocs.
SUMMARY OF THE INVENTION
The substitution of a single Ga-atom or single Ge-atom (GaAl12 and GeAl12 respectively) into the center of an aluminum Keggin polycation (Al13) produces an optimal water-treatment product for neutralization and coagulation of anionic contaminants in water, and producing cleaner water. GaAl12 consistently shows  ̃1 order of magnitude increase in pathogen reduction, compared to Al13. At a concentration of 2 ppm, GaAl12 performs equivalently to 40 ppm alum, removing  ̃90% of the dissolved organic material. The substituted GaAl12 product also offers extended shelf-life and consistent performance. We also synthesized a related polyaluminum chloride compound made of pre-hydrolyzed dissolved alumina clusters of [GaO4Al12(OH)24(H2O)12]7+.



BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form part of the specification, illustrate various examples of the present invention and, together with the detailed description, serve to explain the principles of the invention.
FIG. 1. Ball-and-stick model of the ε-Keggin ion: [MO4Al12(OH)24(H2O)12]x+; M=Ga, Al, Ge, x=7 for M=Al, Ga and x=8 for M=Ge. Solid-state structures of the clusters vary minimally with central metal substitution: For the central MO4 tetrahedron (yellow), M-O  ̃1.83 Å for M=Al, M-O  ̃1.89 Å for M=Ga, and M-O  ̃1.80 Å for M=Ge. All Al—O bond lengths of the octahedral aluminum (turquoise) vary from  ̃1.8-2.0 Å for all three compositions, Al13, GaAl12 and GeAl12.
FIG. 2. MS-2 bacteriophage population reduction by GaAl12, Al13 and GeAl12. MS-2 population in controls: for 34 mg/L Al dose, 7.50×108 pfu/ml; for 10 mg/L dose, 9.83×107 pfu/ml; for 2 & 5 mg/L doses, 1.27×108 pfu/ml. Error bars indicate range on 2-3 replications.
FIG. 3. Inactivation of native wild-type bacteriophages in Rio Grande water (Albuquerque, N. Mex., USA); comparing the efficacy of alum, GeAl12, Al13 and GaAl12. Error bars indicate range on two replications.
FIG. 4. TEM image of MS-2 bacteriophage in a GaAl12 floc matrix. (Uranyl acetate stained).
FIG. 5. 27Al MAS NMR spectrum of MS-2-Al13 floc showing the preservation of Al13 and Al30 clusters in the coagulated matrix.



DETAILED DESCRIPTION OF THE INVENTION
The most effective commercially available coagulant for pathogen removal is known as PACl, or polyaluminum chloride. Polyaluminum chloride contains a variety of pre-hydrolyzed dissolved alumina clusters; Al13, or [AlO4Al12(OH)24(H2O)12]7+ in particular. We have found that alumina based coagulants for pathogen mitigation, water clarification and removal of organic contaminants from water via coagulation are enhanced by introducing a small amount of gallium into the hydrolyzed alumina. We have synthesized a related compound GaAl12 by substitution of a Ga to form [GaO4Al12(OH)24(H2O)12]7+. The Al13-Keggin ion for neutralization and coagulation of anionic contaminants in water is even more effective with Gallium (Ga) or Germanium (Ge) substituted in the central-site of the molecule.
Unexpectedly, we found that the substituted molecule, GaAl12, is more effective than Al13 by approximately an order of magnitude for removing pathogens, and it outperforms common coagulants; ferric chloride, alum and the Al13-based products, in all tests including water clarification, removal of dissolved organic substances, and minimal residual aluminum. GaAl12, also has improved shelf-life over Al13. Furthermore, with the improved performance, less coagulant and coagulant aids are necessary, improving the affordability of this optimized alumina coagulant.
GaAl12 and Al13 are generally referred to as alumina Keggin ions, and the GaAl12 Keggin ion is more stable than the Al13 Keggin ion. This stabilization results in better efficacy in removing cultured model bacteriophage from laboratory solutions (Table 1) and wild-type bacteriophage from river water (Table 2). In Table 2, the performance of GaAl12 (and Al13) is also compared to that of alum, a commonly used coagulant. GaAl12 consistently shows  ̃1 order of magnitude increase in pathogen reduction, compared to Al13. Table 3 shows the results of water clarification studies, comparing GaAl12 to the Al13, alum and ferric chloride (another commonly-used coagulant). The EPA standard for drinking water is 0.3 nepholometric turbidity units (NTU); so GaAl12 is the only coagulant we tested that meets this standard, other than ferric chloride. Oftentimes it is necessary to add a coagulant aid such as an anionic polymer, but this is not the case with GaAl12. In Table 4, we show the removal of dissolved organic contaminants, comparing the GaAl12 coagulant to Al13 and alum. The A254 method is used here; where concentration of unsaturated carbons and aromatic carbons (generically referred to as humic substance) is quantified via the 254 nm adsorption in the UV spectrum.
These results show that a concentration of 2 ppm GaAl12 performs equivalently to 40 ppm alum, removing  ̃90% of the dissolved organic material. Additionally, 5 ppm GaAl12 coagulant removes  ̃20% more humic substance than the same amount of Al13 coagulant. Also listed in Table 4 is the residual aluminum, post-treatment. While all coagulants tested fall within the EPA range (EPA standard for residual aluminum is 0.05-0.2 ppm); the GaAl12 again is superior with the lowest Al concentration.
Another advantage offered by GaAl12 over Al13 is longer shelf-life, and consistent performance of the product. Al13 destabilizes by aggregation and eventual precipitation of larger oligomers. GaAl12 does not undergo this process (determined by light scattering experiments of solutions, as well as ESI-MS—electrospray ionization mass spectroscopy). Therefore the composition, concentration and species distribution remains constant longer, which are all important parameters for consistent water treatment performance.
Preparation of pure GeAl12, Al13 and GaAl12 solutions. Crystalline salts of Na[AlO4Al12(OH)24(H2O)12(SO4)4].xH2O, [GeO4Al12(OH)24(H2O)12](SO4)4.14H2O and Na[GaO4Al12(OH)24(H2O)12(SO4)4].xH2O, were synthesized by literature methods. Cluster solutions were obtained by BaSO4 metathesis, using either BaCl2 or Ba(NO3)2. For example, 1 gram of [GeO4Al12(OH)24(H2O)12](SeO4)4.14H2O and 0.43 grams of BaCl2 are ground in methanol until dry, using mortar and pestle. The powder is placed in 10 ml DI water and stirred for two hours, centrifuged, 0.2 micron-filtered, then immediately diluted by 10× to avoid precipitation. Appropriate dilutions for experiments are done after Al analysis by either a Hach assay or ICP-MS (PerkinElmer, Elan 6100).
Synthesis of Al13 and GaAl12 solutions. Water treatment experiments were also carried out with “crude” Al13 or GaAl12 solutions, to determine if the metathesis “purification” was beneficial in practical applications. For GaAl12: 0.4 grams NaOH is added to 50 ml DI H2O. Anhydrous GaCl3 (0.28 g) is added to the NaOH solution. AlCl3.6H2O (4.83 grams) is dissolved in 100 ml DI H2O (in 250 ml Erlenmeyer flask). The aluminum chloride solution is stirred ( ̃300 RPM) at 90° C. A 50-ml plastic syringe is loaded with the prepared NaOH/GaCl3 solution and dispensed by syringe pump at a rate of 20 ml/hr. After the hydrolysis step (approx. 2.5 hrs), the solution is heated and stirred for an additional 9.5 hrs. The solution is then checked by 71Ga NMR (δ=138 ppm) to confirm the Keggin ion is formed, and by ICP-MS to determine concentration of aluminum. 27Al NMR of these solutions confirmed that essentially no Al13 was formed, indicated by the absence of the δ=62 ppm peak. The Al13 solution was prepared in an identical manner; but without the addition of the gallium salt, and the post-heating step was carried out for only 30 minutes. These solutions were checked by 27Al NMR (δ=62 ppm for the tetrahedral AlO4-site, and usually some monomer at δ ̃0 ppm was also observed).
Preparation of Alumina Flocs. Model Gels or Flocs were Prepared by Addition of an alumina solution; alum, Al13 or GaAl12 to a 0.05 M HNaCO3 buffered solution with a starting pH of around 8.3. A crude 0.1 M Al solution (30 ml) of Al13 or GaAl12 was added to 500 ml HNaCO3 solution while stirring at room temperature at 300 rpm. A floc or precipitate was observed immediately and the solution stirred for 20 minutes more. For the alumina floc from alum, a 0.03 molar solution was utilized due to the lower solubility; and the rest of the procedure was the same. These flocs were isolated by centrifugation, and washing with DI water. Finally, the alumina flocs were dried in a vacuum oven at 70° C. overnight. The glassy powders were ground with a mortar and pestle into a powder for further characterization.
27Al MAS NMR experiments of the alumina flocs were performed on a Bruker Avance 600 instrument at an 27Al frequency of 156.38 MHz. Chemical shifts were referenced to 1M aluminum nitrate, δ=0.0 ppm. Spinning speed was 15 khz.
71Ga MAS NMR experiments. All NMR experiments were performed on a Bruker Avance 600 instrument at a 71Ga frequency of 183.13 MHz. Chemical shifts were referenced to 1M Ga(H2O)6+, δ=0.0 ppm. Spinning speed was 12.5 kHz, DMFIT was used for deconvolutions.
TEM. Samples were diluted in PBS and mounted onto 6-nm thick carbon films supported by tabbed copper grids. Incubation proceeded for five minutes, followed by sample removal by blotting with Whatman #1 filter paper until either a thin film remained (for negative staining) or until dry (direct imaging). Negative staining of the samples consisted of incubating the grids on droplets of 2% uranyl acetate in water for two minutes, then blotting away the stain and drying. Dried tabs were removed from the grids, then the samples were imaged in a Hitachi H7500 transmission electron microscope and an Advanced Microscopy Techniques XR60 bottom mount camera.
ESI-MS data was acquired on an Agilent 1956b single-quadrupole mass spectrometer at a cone voltage of −20 V. Freshly prepared samples were introduced at 20 μl/min using a syringe pump.
Cultivation of infectious agents. Escherichia coli strain C3000, from American Type Culture Collection (ATCC), was maintained for up to six serial passages at 36°±1° C. either in tryptic soy broth (TSB) or on agar (TSA, 1.4% agar).
The MS-2 bacteriophage (ATCC strain 15597-B1TM) used in viral clearance experiments, was reconstituted according to ATCC instructions and expanded into an early log-phase E. coli culture to produce a high-titer seed stock. The concentration of plaque forming units (pfu) in the broth was determined after 0.22-micron filtration, using the double agar layer assay described below, and was adjusted to approximately 2×101° pfu mL−1 with Dulbecco's phosphate buffered saline (DPBS) before freezing aliquots at −20° C.
For analysis by NMR and TEM, MS-2 propagation was scaled to 200 mL. Virus-rich filtrate was dialyzed against 50 volumes of deionized water containing 0.01% NaN3, using Spectra/Por® 2 membranes (Spectrum, 12,000-14,000 mwco). Viral particles, along with any remaining polypeptides from TSB, were precipitated by adding aluminum clusters with slow stirring to obtain 40 ppm aluminum. After 14-16 hours at 4° C., precipitates were twice centrifuged and washed with deionized water, and remained in aqueous suspension for TEM or were freeze-dried for NMR.
Native coliphages were isolated from 0.22 micron-filtered water collected from the Rio Grande. Initially, the river water was subjected to a plaque assay with E. coli host. From the resulting petri dishes, 25 plaques were selected at random, pooled in 5 mL of DPBS with vigorous agitation, and the supernatant was 0.22 micron-filtered. The presumably heterogeneous isolate population was expanded in an E. coli broth culture, yielding a working stock of wild type coliphages that retained consistent viability under refrigeration.
Double Agar Layer Plaque Assay (plaque assay). Plaque assays were performed as described in the USEPA Manual of Methods for Virology. Briefly, test samples were diluted in sterile DBSS, with a target of 100-300 pfu mL−1, and combined with E. coli host cells in soft TSA (0.7% agar) at 44±1° C. The molten mixture was layered onto standard TSA in a 100 mm petri dish and allowed to solidify. Plaques were counted after 14 to 16 hours of incubation.
Cryptosporidium parvum. Coagulants were compared to demonstrate their ability to flocculate and remove irradiated C. parvum oocysts (BTF, Sydney, Australia) from Rio Grande water by sedimentation. Duplicate vials of 0.22-micron filtered, but otherwise untreated, water at pH 8.1 were seeded at 1.0×107 mL−1 and dosed with specified coagulants at 10 mg/L Al or Fe. Vials were mixed by inversion initially and every five minutes for 15 minutes, then allowed to settle for 15 minutes, after which 10-μL samples were withdrawn from the center of each vial. Oocyst concentrations were determined microscopically using a hemacytometer.
Water Treatment Experiments. The efficacy of aluminum clusters in viral clearance was tested in sterile centrifuge tubes. Coagulant solutions and MS-2 bacteriophages were added to deionized water to achieve specified concentrations of aluminum and 0.8 to 1.3×108 pfu/ml. After mixing by inversion, each treatment or control mixture was allowed to react for 10 minutes, followed by a five minute, 1200 rcf centrifugation. While ineffective on individual virus particles, the gentle centrifugation settled any flocs. Experiments using native coliphages were in 0.22 micron-filtered river water and a starting load of 0.5 to 0.7×108 pfu/ml. Supernatants from replicate tubes for each treatment were tested using the plaque assay.
Rio Grande Water. Water was collected at a diversion dam for the San Juan-Chama Drinking Water Project (Albuquerque, N. Mex.) in April, 2008. Water conditions were recorded as follows: pre-settled turbidity =121 ntu; turbidity post-24 hr settling=63 ntu; TOC=4.5 ppm; TDS=177 ppm; pH  ̃8.1, total alkalinity 89 mg/mL.
Experiments to evaluate the clearance of turbidity and dissolved organic contaminants (DOC) utilized settled river water. Flasks for testing treatment conditions each contained 200 mL of raw water to which coagulant concentrates were added with slow stirring (30 rpm) and pH 8.1 was measured. Stirring was discontinued after 10 minutes and any flocculation was allowed to settle for 20 minutes. In lieu of sand filtration, typical in post-coagulation processes, the samples were gravity-fed through qualitative filter paper (Whatman, No. 1), and analyzed by turbidimiter (Hach model 2100P), by absorbance at 254 nm (Shimadzu UV-3600) for DOCS).
Contaminant Removal Studies with GeAl12 Al13 or GaAl12 
MS-2 bacteriophage. The first set of tests for contaminant removal was carried out in a controlled laboratory media; DI water with PBS buffer, using the MS-2 bacteriophage as a model virus. MS-2 is commonly used to model viruses in water treatment studies. FIG. 2 shows the log reduction of MS-2 ( ̃108 titer) by ion dosage (2, 5, 10 and 34 mg/L Al). The dosages of both MS-2 and the various aluminum clusters were optimized to quantify differences in the performance of the three clusters, which were remarkable. Unexpectedly, we found that GaAl12 is capable of reducing the MS-2 population at a dose of 2 mg/L Al; while Al13 requires a dose of at least 5 mg/L Al to achieve similar population reductions, and GeAl12 requires a dose equivalent of 10 mg/L Al. (NOTE: for these studies and others reported below, all Al concentrations are normalized to account for differences in GeAl12, Al13 and GaAl12 stoichiometries so that identical Keggin ion concentrations are compared.) The difference in performance between the Keggin clusters diminishes with increasing cluster dose. For example, at 34 mg/L Al, the performance of Al13 approaches that of GaAI12, only about half an order of magnitude less effective in log reduction, perhaps indicating some sweep flocculation in addition to charge-neutralization as the mechanism of virus removal at higher Keggin ion doses.
Wild-type bacteriophage. Native wild-type bacteriophages were isolated from raw river water from the Rio Grande, Albuquerque, N. Mex., the population was expanded on an E. Coli host, and then reintroduced to the river water at a concentration of 5×107 pfu/ml (see experimental). These river water samples were then dosed with 10 mg/L Al solutions, and the log-reduction of the wild-type bacteriophage was quantified (see FIG. 3). In this study, alum (10 mg/L Al) was utilized in parallel, for comparison to the Keggin ion coagulants. Consistent with the MS-2 studies, the ability of the coagulants to reduce the bacteriophage population is: GaAl12>Al13>GeAl12>alum and spans 3.5 orders of magnitude; ranging from  ̃2-log reduction for alum to  ̃5-log reduction for GaAl12.
Cryptosporidium parvum. In Table 5, we compare the use of coagulants GaAl12, Al13, GeAl12, ferric or alum at 10 mg/L metal dose to cryptosporidium-spike raw river water (1.02×107/ml). In this study, alum performed significantly worse than the other coagulants, with only 17.5% removal of the Cryptosporidium. The three Keggin ions exhibited the consistent trend of GaAl12>Al13>GeAl12, but there was little difference between the three coagulants when described as %-removal. The ferric did not perform quite as well as the Keggin ions, but significantly better than the alum. This study had particular significance in that Cryptosporidium is infamous for its resistance to chlorination, and thus it is especially important to demonstrate that its removal can be accomplished by front-end water treatment technologies.
Turbidity. Removal of turbidity in Rio Grande water (predominantly due to clay particles) resulting in water clarification also trended as GaAl12>Al13>GeAl12 (see Table 5). For this test, the standard ferric performed best, but GaAl12 was comparable; and only GaAl12 and ferric chloride met EPA standards for drinking water without further treatment.
Dissolved Organic Carbon. Unexpectedly, GaAl12 also exhibited superior performance in removing dissolved organic carbon (DOC) from humic-acid-spiked Rio Grande water, compared to GeAl12, Al13, alum or ferric. (Table 6) In a second series of tests investigating just the performance of GaAl12, the pH of the Rio Grande water was pre-adjusted, varying from 6.2 to 8.2, to determine its working range. In most tests, the GaAl12 at 5 mg/L removed around 88% DOC. At the lowest pH values, lime was required for flocculation to occur, and the DOC removal dropped slightly to around 85%.
ESI-MS Studies of Aqueous GeAI12, Al13 and GaAl12 
In all water purification tests described above, the efficacy ranking of the aluminum clusters is GaAl12>Al13>GeAl12. This was initially surprising, in that GeAl12 has the highest charge of the three clusters in the solid-state; and the presumed mechanism of contaminant removal is by charge-neutralization, which tends to scale with ion charge. However, to understand this data, we need to consider the state of the clusters in aqueous solution. The aluminum clusters are fluxional in aqueous solution. They are generally acidic. Self-buffering pH of freshly extracted 0.1 M solutions of GaAl12, Al13 and GeAl12 are 4.58, 4.47 and 4.37, respectively. They can both protonate at the hydroxyl ligand and deprotonate at the water ligand, as well as aggregate, which usually involves dehydration or deprotonation.
Electrospray Ionization Mass Spectrometry (ESI-MS) of solutions of GaAl12, Al13 or GeAl12 revealed differences in the three clusters when otherwise identical solutions were ionized under the same conditions. Similar to aqueous behavior, deprotonation of the clusters is the major reaction, and the ESI-MS behavior is qualitatively consistent with the aqueous reactivity. The major ionic species of GaAl12, Al13 and GeAl12 observed by ESI-MS are summarized in Table 7. The aluminum clusters undergo some association with sodium and nitrate ions; but overall, these ion pairs do not dominate the spectra. The major species of GaAl12, Al13 and GeAl12 observed by ESI-MS have generally undergone 3-8 deprotonation steps; and the cluster charges, not including associated NO3− or Na+ ions, range from 0 to 4+. The three most abundant species of GaAl12, Al13 and GeAl12 have undergone 3-4, 4-6, and 6-8 deprotonation steps, respectively, which is in qualitative agreement with aqueous acidities: GeAl12>Al13>GaAl12.
In the Al13 solution (Table 7), we also observe a small amount of the higher oligomer, the Al30 polycation. There is no evidence, from repeated attempts to make a Ga- or Ge-centered analogue of the Al30 that such higher oligomers exist without an aluminum core. However, broad humps are observed in the GeAl12 spectrum in the approximate spectral region of the higher oligomer, as well as peak clusters that are less well-defined, that may indicate a mixture of species as a result of the GeAl12 relative instability (see supplementary information). The effect of larger polycations or colloids on water treatments has not been well-studied. It was suggested in one report that higher Al30 content in PACl solutions is linked to improved water clarification, but no studies to our knowledge have been reported on the efficacy in removal of contaminants such as DOC or microbes.
The aggregation of Al13 in solution, forming larger polycations or colloids; has been detected via light scattering of aged solutions. By dynamic light scattering, we do observe aggregation in the Al13 solution but never in the equivalent solutions of GeAl12 or GaAl12. A solution of Al13 shows clusters of 700-900 nm in diameter after just 12 hours aging at room temperature, which can be eliminated by either centrifugation or filtration. The oligomerization and colloid formation in Al13 solutions is very likely the cause of limited shelf-life of PACl. As the clusters become larger, their effective charge-to-size ratio becomes less, diminishing their ability to charge-neutralize anionic contaminants. As the large clusters precipitate as colloids, the Al-concentration becomes less, also decreasing the contaminant removal efficacy with time.
To summarize the aqueous state of GaAl12, Al13 and GeAl12 in relation to their performance in the water treatment studies: 1) the aqueous charge of the species due to their acidity trends: GaAl12>Al13>GeAl12, which is the same as their contaminant removal efficacy, and 2) Al13 is also less effective than GaAl12 due to its tendency to form Al30 and larger colloids. Surprisingly, by several lines of evidence, GaAl12 does not appear to undergo this process. Its ESI spectrum is ‘clean’ in the higher oligomer region, and it does not show colloidal growth by light-scattering studies. 3) GeAl12 is both the most acidic and has evidence of oligomerization in the ESI spectrum, contributing to its poorer ability to neutralize anionic contaminants in water purification studies.
Solid-state Characterization of Alumina Flocs.
FIG. 4 shows TEM images of an MS-2-GaAl12 precipitate, in which there is a significantly high virus particle-to-MAl12 (M=Ga, Al) ratio so that neutralization of the virus particle dominates over polymerization of the Al13 or GaAl12 polycations. In these images, we observe the fractal-type growth of the alumina precipitate, that has been described by prior small-angle X-ray scattering studies. Solid-state 27Al MAS NMR spectroscopy was used to identify the alumina species that adhere and flocculate the MS-2 virus.
FIG. 5 shows a 27Al MAS NMR of MS-2 neutralized by an Al13 solution. The spectrum shows that the Keggin ions are remarkably well-preserved in the MS-2-Al13 floc, consistent with other studies. The AlO4 central tetrahedral site of the MS-2-Al13 floc is δ=63.09 ppm, with a line width of 528 Hz. The AlO4 peak of the Na[AlO4Al12(OH)24(H2O)12][SO4]4.xH2O Keggin salt is δ=62.58 ppm, with a line width of 151 Hz. The small peak at 69 ppm in the MS-2-Al13 floc is the tetrahedral site of Al30, qualitatively consistent with the aluminum species populations observed by ESI-MS in the Al13 solution. The octahedral aluminum peak of the MS-2-Al13 floc is modeled as three peaks at 4.9, −3.4 and −17.6 ppm (standard Al13 Keggin salt: δ=9.87, 9.95 and 13.97 ppm). For both the MS-2-Al13 floc and the crystalline salt standard, the relative weight of the two peaks are both 10% tetrahedral and 90% octahedral, compared to the theoretical 8% tetrahedral and 92% octahedral for the 1:12 ratio of the Keggin ion. This slight discrepancy is likely due to differences in different relaxation rates of the two sites.
Since the soluble polycation species detected in the treatment solution match the building blocks of the floc that neutralizes and precipitates the MS-2; this provides evidence that these soluble polycations are indeed effective active ingredients of aluminum coagulants that partake in neutralization of the anionic contaminants.
An identical experiment of MS-2 neutralization/precipitation was also carried out using GaAl12. This study similarly showed the broad octahedral aluminum peaks by 27Al NMR, and no tetrahedral peaks. Unfortunately, we could not observe the GaO4 by 71Ga NMR in the MS-2-GaAl12 floc: the sample size was too small with the Ga quite dilute, in addition to the NMR signal being greatly diminished by distortion of the polyhedron upon neutralization and precipitation of MS-2.
We also precipitated alumina flocs in a dilute carbonate buffer solution (without added contaminants) in order to compare the precipitates from alum, Al13 and GaAl12. In these studies, we added the alum, Al13 or GaAl12-containing solutions to the buffer solution (pH  ̃8.3), rather than adding base to the alumina solutions, as was done in most prior studies on characterization of alumina gels. This was to more closely simulate a water treatment scenario, in which alum or PACl is added to raw water that has a higher pH (generally 6.5-8.5) than aqueous alumina solutions. The chemical shifts and ratios are reported in Table 4; and distinct differences are observed. All 27Al MAS NMR spectra, of course, are dominated by the octahedral aluminum peak, between 4-8 ppm. These are broad peaks that can be deconvoluted into several smaller peaks, but for comparison purposes we report them as a single peak in Table 8.
The Al13 precipitate, similar to the MS-2-Al13 precipitate, has both the Al13 and Al30 AlO4 site. However, they are present in approximately equal amounts. The solution from which this solid was precipitated was more aged, so conversion of Al13 to Al30 is indeed an issue to consider in the shelf-life of Al13, or PACl solutions for water treatment. Very little 5-coordinate aluminum is observed. The 71Ga MAS NMR of the GaAl12 precipitate has only one tetrahedral peak at δ=129 ppm, compared to the previously reported peak at δ=122 ppm for similarly-prepared gels. Both the GaAl12 and alum 27Al NMR spectra have a single tetrahedral (δ=67.6 ppm) and 5-coodinate (δ=35.0 ppm) aluminum peak, with alum having a greater percentage of both. By the position of the tetrahedral peak, it is clearly not an Al13-like specie, nor an Al30-like specie. The small amount of 4-coordinate and 5-coordinate aluminum from the GaAl12 (total=11%) likely comes from either 1) colloidal alumina present in the ‘crude solution’ rather than from the Keggin ions; in that preparation of this solution involves extensive heating (9.5 hours) at 90° C.; or 2) monomeric aluminum: 27Al NMR of the crude GaAl12 solution does have a monomeric Al(H2O)6 peak.
To summarize the MAS NMR study of the alumina flocs, all of the tetrahedral, 5-coordinate and octahedral species observed in the alum precipitate are derived from monomeric ([Al(H2O)6] aluminum, and the tetrahedral site observed is not indicative of the Al13 Keggin ion. Both the Al13 and GaAl12 precipitates reflect preservation of the Keggin ions, and the Al30 ion, resulting from aging of the Al13 solution. Conversion of Al13 to Al30, and then larger colloids, observed throughout this study, clearly affects the shelf life of PACl water-treatment solutions. There is no evidence for GaAl12 undergoing this reaction, which may be one key to its surprisingly improved ability to neutralize and precipitate anionic contaminants.
Regarding the issue of Al30 as an effective contaminant-neutralization ion; our studies indicated qualitatively that Al30 is less effective than the Keggin ion. We observed that as Al13 solutions age, they became less effective, and contained more Al30. We also note that Al13 solutions lose soluble aluminum with time, reflected in ICP MS analyses, which is probably due to the conversion of Al30 to larger colloids that precipitate.
Small differences in the efficacy of water-treatment technologies at low cost can potentially mean more reliable treatment of challenged water supplies. Here we show that a single-atom substitution in the common molecule in water treatment coagulants (PACl) markedly enhances contaminant-removal performance and improves shelf life. The GaAl12 has proven a superior coagulant reagent in every single test due to its kinetic stability high charge in aqueous media: both in its lower acidity and tendancy not to form larger clusters and oligomers. The extra cost of producing GaAl12 is likely not much more than the cost of producing PACl, since a small amount of Ga (<8%) is needed on a per-molecule basis. Similarly the labor involved in preparing crude GaAl12 is comparable to producing PACl. Furthermore, gallium is innocuous, as well as sequestered in the core of the cluster with no contact to the surrounding aqueous medium. Additionally, cost savings in its usage are potentially recovered since our studies show the improved efficacy and shelf-life of GaAl12-based additives means lower dose rates per volume of water treated. Finally, stability and thus contaminant removal efficacy of the aluminum Keggin cluster is compromised by increased cluster charge, as seen in the case of GeAl12.
In summary, the present invention has the following advantages over the commercial coagulant agents now in common use, such as ferric chloride, alum, and polyaluminum chloride. Those advantages include: (a) efficacy under a wider range of naturally occurring conditions, including pH, temperature and alkalinity; (b) greater effectiveness in waters of high pH (pH 6.3 to 8.2) without adjustment; (c) doesn't require lime supplementation, and is more effective in softer water than is alum; (d) greater stability and longer shelf life than obtained with alum or polyaluminum chloride; (e) does not stain treatment equipment as do ferric compounds; and (f) comprised of well-defined, monospecific molecular species, unlike the variable mixtures present in polyaluminum chloride products.
As for operating ranges, the compounds of the present invention are most efficacious in a pH range of 6.3 to 8.0 without pH adjustment, and can be useful at lower pH if calcium is present at one millimolar concentration or higher. GaAl12 performs well in alkalinity conditions of trace to 400 mg/L (as CaCO3). Coagulation is effective at temperatures of 5 to 40 degrees C., although below 10 C it benefits from the addition of a polymeric flocculation aid (as do other coagulants).







TABLE 1







Comparison of Al13 and GaAl12 coagulants for removal of MS-2


Bacteriophage from Laboratory Solutions
















Al
Dilution



Log




concentration
for
Raw
Total
Mean
Reduction


Reaction
Coagulant*
(ppm)
Plate
cfu
pfu/mL
pfu/mL
Value

















A
Control
N/A
5.00E+05
64
3.20E+07
3.65E+07
N/A






82
4.10E+07




B
Al13
34
1.00E+01
4
4.00E+01
2.50E+01
6






1
1.00E+01




C
GaAl12
34
1.00E+01
2
2.00E+01
1.00E+01
7






0
0.00E+00




D
control
N/A
8.00E+05
997
7.98E+08
7.50E+08
N/A






878
7.02E+08




E
Al13
34
1.00E+01
205
2.05E+03
1.61E+03
5.67






116
1.16E+03




F
GaAl12
34
1.00E+01
70
7.00E+02
4.55E+02
6.22






21
2.10E+02




G
Control
N/A
5.00E+05
203
1.02E+08
9.83E+07
N/A






208
1.04E+08








179
8.95E+07




H
Al13
10
5.00E+01
30
1.50E+03
1.55E+03
4.80






30
1.50E+03








33
1.65E+03




I
GaAl12
10
1.00E+01
20
2.00E+02
2.10E+02
5.67






23
2.30E+02








20
2.00E+02





*two or three replications for each experiment













TABLE 2







Comparison of Al13, GaAl12, and alum coagulants for removal of wild-type


bacteriophage from Rio Grande water
















Al




Log




concentration
Dilution 
Raw
Total
Mean
Reduction


reaction
Coagulant*
(ppm)
for Plate
cfu
pfu/mL
pfu/mL
Value

















A
control
N/A
5.00E+05
100
5.00E+07
5.23E+07
N/A





5.00E+05
109
5.45E+07




B
Al13
10
1.00E+02
61
6.10E+03
5.90E+03
3.95



Al13
10
1.00E+02
57
5.70E+03




C
GaAl12
10
1.00E+02
2
2.00E+02
4.00E+02
5.12



GaAl12
10
1.00E+02
6
6.00E+02




D
alum
10
1.00E+03
790
7.90E+05
7.74E+05
1.83
















TABLE 3







Clarification of Rio Grande water by GaAl12 coagulant 


compared to Al13, alum, and ferric chloride









Coagulant/concentration
pH
Turbidity (NTU*)





Control (raw river water- 
8.18
54  


no coagulant)




Ferric Chloride/10 ppm
6.48
0.16


Alum/10 ppm
6.65
0.49


Al13/10 ppm
7.50
1.26


GaAl12/10 ppm
6.24
0.19





*nepholometric turbidity units













TABLE 4







Removal of Dissolved Organic Contaminants* from Rio Grande Water by


GaAl12, Compared to Al13 and Alum

















UV
Humic
Lime

Residual





adsorp-
acid
needed for 

alumi-


Coagu-
Concentra-
pH after
tion (254
equiv.
pH adjust-
%
num


lant
tion (ppm)
treatment
nm)
(mg/L)
ment
removal
(ICP-MS)

















None
N/A
8.21
0.113
3.94
no
N/A
0.112


(natural)









None
N/A
8.2
0.252
8.85
no
N/A



(humic









acid









spiked)









Alum
5
7.3
0.108
3.76
no
58%



Alum
10
7.0
0.078
2.70
no
69%



Alum
20
6.7
0.050
1.71
no
81%



Alum
40
6.5
0.043
1.46
yes
83%
0.085


Al13
5
7.9
0.075
2.59
no
71%
0.049


GaAl12
2
6.3
0.035
1.18
no
87%
0.033


GaAl12
5
6.2
0.027
0.90
yes
90%
0.042





*spiked with humic acid













TABLE 5







Comparison of Coagulants for Cryptosporidium parvum


(C. parvum) and Turbidity Removal












C. 
Percent





parvum
removal





concentration
of C.

Turbidity


Coagulant/concentration
(per mL)
parvum
pH
(NTU)*





EPA standard for



0.3§


turbidity






Control (raw river 
1.02 × 107
N/A
8.13
54  


water, no coagulant)






Ferric chloride/10 mg/L 
7.98 × 105
92.2
6.80
0.16


Alum/10 mg/L
8.42 × 106
17.5
6.75
0.49


GeAl12/10 mg/L
3.07 ×105
97.0
7.48
3.38


Al13/10 mg/L
1.29 × 105
98.7
7.56
1.26


GaAl12/10 mg/L
1.10 × 105
98.9
7.50
0.19





*nephelometric turbidity units


§95% of NTU readings of finished water must be 0.3; and cannot go above 1.0













TABLE 6







GeAl12, Al13 and GaAl12 Coagulants for Dissolved 


Organic Contaminant Removal from River Water












Concen-

Treatment at 5° C.
Treatment at 21° C.














tration
Resulting
Abs.
DOC
Abs.
DOC


Coagulant
mg/L
pH
254 nm
mg/L*
254 nm
mg/L
















Untreated
NA
8.1






Water








GeAl12
5
7.7
0.057
1.94
0.051
1.71


Al13
5
7.8
0.056
1.88
0.044
1.46


GaAl12
5
7.7
0.042
1.40
0.038
1.24


Alum
5
7.0
0.071
2.44
0.068
2.32


FeCl3
5
7.2
0.106
3.67
0.101
3.49





*DOC equivalent to mg/L humic acid, based on a standard curve of humic acid obtained from Alpha Aesar.













TABLE 7







Dominant ions§ detected by ESI-MS in aqueous solution 


of GaAl12, Al13 and GeAl12











Number of




deprotonation




steps from




parent


Specie
m/z
cluster*












GaAl12




[GaAl12O5(OH)26]3+
311
4


[GaAl12O4(OH)27(NO3)]3+
326
3


[GaAl12O5(OH)26(NO3)]2+
488
4


[GaAl12O5(OH)27]2+
466
5


[GaAl12O4(OH)30(H2O)3Na]2+
522
6


Al13




[A113O4(OH)28]3+
297
4


[Na2A113O6(OH)26]3+
312
6


[A113O4(OH)29(H2O)2]2+
472
5


[Na2Al13O5(OH)29]2+
485
7


[A130O8(OH)64(H2O)10(NO3)6]4+
645
8


GeAl12




[GeAl12O7(OH)23(H2O)]3+
306
6


[GeAl12O4(OH)30(H2O)]2+
495
6


[GeAl12O8(OH)21(NO3)]2+
472
8


[GeAl12O4(OH)29(H2O)5]3+
348
5





§The most abundant specie for each dehydration series observed (see text).


*MAl12(O)4+x(OH)24+y (M = Ga, Al, Ge)


one deprotonation for each y: H2O → OH− + H+


two deprotonation for each x: H2O → OH− + H+


OH− → O2− + H+













TABLE 8







MAS NMR (71Ga and 27Al) peaks observed for Al13, GaAl12 


and alum precipitates.











Al13
GaAl12
alum













neutralized

neutralized





MS-2¥
Floc
MS-2¥
Floc
Floc















Tetrahedral







δ (ppm)

63.6
N/A§
129



%

 5.4

(71Ga NMR)



δ (ppm)
63.1
70  

67.6
67.6


%
10
 5.6

 6.2
 8.5


5-coordinate







δ (ppm)

34.8
none
35.0
35.0


%
none
 1.4

 5.0
 9.8


Octahedral







δ (ppm)
4.9
 8.0 
  8.9
 8.9
 8.0


%
90
87.6 
100
88.8
81.7





§GaO4 site too distorted and dilute to observe by 71Ga NMR; no 27Al tetrahedral sites observed


¥MS-2 bacteriophage neutralized and precipitated by Al13 or GaAl12.

## Claims

1. A method of removing anionic contaminants from contaminated water, comprising adding at least 2 ppm of a GaAl12 coagulant to the contaminated water to form flocs; and
removing the flocs from the contaminated water by filtration, thereby producing cleaner water.

2. The method of claim 1, comprising adding no more than 10 ppm of GaAl12 to the contaminated water.

3. The method of claim 1, comprising adding 5 ppm of GaAl12 to the contaminated water.

4. The method of claim 1, wherein the GaAl12 coagulant is in the form of a prehydrolyzed material having the composition [GaAl12O4(OH)24(H2O)12]7+.

5. The method of claim 1, wherein the pH of the contaminated water to be treated is in the range of 6.3 to 8.2.

6. The method of claim 1, wherein the method does not comprise adding lime supplementation.

7. The method of claim 1, wherein the contaminated water to be treated has an alkalinity of up to 400 mg/L as CaCO3.

8. The method of claim 1, further comprising adding a polymeric flocculation aid at water temperatures below 10 C.

9. The method of claim 1, further comprising adding calcium to the contaminated water at a concentration of at least 1 millimolar, when the pH of the water is less than 6.3.

10. A method of removing anionic contaminants from contaminated water, comprising adding at least 2 ppm of a GeAl12 coagulant to the contaminated water to form flocs; and
removing the flocs from the contaminated water by filtration, thereby producing cleaner water.

11. The method of claim 10, comprising adding no more than 10 ppm of GeAl12 to the contaminated water.

12. The method of claim 10, comprising adding 5 ppm of GeAl12 to the contaminated water.

13. The method of claim 10, wherein the GeAl12 coagulant is in the form of a prehydrolyzed material having the composition [GaAl12O4(OH)24(H2O)12]8+.

14. A method of removing anionic contaminants from contaminated water, comprising adding 2-10 ppm of GaAl12 coagulant to the contaminated water, forming flocs, and then removing the flocs from the contaminated water by filtration, thereby producing cleaner water.

15. The method of claim 14, wherein the pH of the contaminated water to be treated is in the range of 6.3 to 8.2.

16. The method of claim 14, wherein the method does not comprise adding lime supplementation.

17. The method of claim 14, wherein the contaminated water to be treated has an alkalinity of up to 400 mg/L as CaCO3.

18. The method of claim 14, further comprising adding a polymeric flocculation aid at water temperatures below 10 C.

19. The method of claim 14, further comprising adding calcium to the contaminated water at a concentration of at least 1 millimolar, when the pH of the water is less than 6.3.