1. Adelia J. A. Aquino Institute for Theoretical Chemistry und Structural Biology, University of Vienna and Institute of Soil Research, University of Natural Resources and Applied Life Sciences Vienna - Vienna, Austria MODELING OF THE SURFACE OF THE MINERAL GOETHITE

2. OUTLINE A.GOETHITE COMPLEXES B.2,4-DICHLOROPHENOXYACETIC ACID HERBICIDE COMPLEXES

3. BACKGROUND Goethite- Hydrated iron oxide Size: 6X8 cm Origin: Brazil Goethite (α-FeOOH) is a common component of soils. It belongs to the group of ferric oxyhydroxides, which are able to sorb large amounts of heavy metal cations, anions and oxyanions and also organic pollutants (e.g. polycyclic aromatic hydrocarbons). The surfaces of ferric oxyhydroxides are predominantly formed from hydroxyl groups. Even though the bulk structure of goethite is relatively simple the surface structure is complicated due to the existence of several types of adsorption surface sites.

4. STUDIED SYSTEMS I- Isolated clusters: Fe 4, Fe 6 and Fe 8 II - Complexes formed of each isolated cluster and water, acetic acid, acetate, 2,4D-diclhorophenoxiacetic acid, 2,4D-diclhorophenoxiacetate III – Fe 6 ···C 6 H 6 GOAL The main aim of the present work is the study of adsorption complexes on goethite. We show the structural manifold of the hydroxyl groups of a goethite surface in their interaction with a set of adsorbents occurring in soil environments. For this purpose we have selected a series of molecular species containing small model molecules like water and acetic acid and acetate representing typical polar interactions in soils. Beyond that the interaction of the herbicide 2,4-dichloro-phenoxyacetic acid (2,4-D) and of benzene with the goethite surface has been studied. The latter choice resulted from the absorption capability of goethite concerning aromatic compounds.

5. STRUCTURAL AND COMPUTATIONAL DETAILS: -The goethite structure consists of a network of distorted octahedra with Fe(III) cations in their centers which are connected via μ-oxo-bridges. -Cluster models used in the calculations were constructed from the (110) slab surface.The surface of this model contains three different OH types. -All calculations were performed at DFT/B3LYP level of theory with the TURBOMOLE program. -SCF calculations for isolated clusters and the water complexes were carried out at low and high-spin as well as at closed shell levels. -Basis Set: SVP, SVP+sp Only the O-H groups highlighted in the cluster model picture were optimized. All other geometric parameters were kept frozen.

6. RESULTS Fe 4 Fe 6 Fe 8

7. Geometrical parameters (in Å) of isolated iron clusters at low spin (LSPIN), high spin (HSPIN) and closed shell (CSHELL) using B3LYP/SVP approach SystemMethodR O 1 -HRO 2 -HRO 3 -HRO 4 -HRO 5 -HRO 6 -HRO 7 -HRO 8 -HRO 9 -H Fe 4 LSPIN0.9690.9710.9680.970 HSPIN0.9690.9710.9700.965 CSHELL 0.973 (0.973) 0.980 (0.977) 0.969 (0.966) 0.966 (0.969) Fe 6 LSPIN0.9840.9710.9680.9670.9690.968 HSPIN0.9880.9720.966 0.9670.969 CSHELL 1.001 (0.999) 0.972 (0.971) 0.969 (0.968) 0.977 (0.973) 0.969 (0.968) 0.979 (0.977) Fe 8 LSPIN0.969 0.9700.9870.9770.972 HSPIN0.967 0.9680.9870.9770.971 CSHELL 0.981 (0.982) 0.977 (0.973) 0.969 (0.967) 0.969 (0.972) 0.977 (0.968) 0.969 (0.967) 0.988 (0.983) 0.975 (0.974) 1.003 (1.006) a values in parentheses are results obtained with the SVP+sp basis set

8. 1b 1c 1d 1a

9. Hydrogen bond distances (Å) between goethite clusters and the water molecule using the B3LYP/SVP approach. a values in parentheses are results obtained with the SVP+sp basis set SystemDistances Fe 4 -H 2 O (Fig. 1a)HBA1HBD1HBD2 Low-Spin1.701.782.44 High-Spin1.701.682.53 Closed Shell a 1.63 (1.76)1.79 (1.81)2.43(2.41) Fe 6 -H 2 O (Fig. 1b) Low-Spin1.761.842.39 High-Spin1.731.842.19 Closed Shell a 1.85 (1.99)1.91 (1.97)2.29 (2.39) Fe 6 -H 2 O (Fig. 1c)HBA1HBA2HBD1 Low-Spin1.601.682.07 High-Spin1.812.051.76 Closed Shell1.84 (1.89)2.19/(2.33)1.76 (1.83 ) Fe 8 -H 2 O (Fig. 1d) Low-Spin1.922.391.71 High-Spin1.952.081.71 Closed Shell a 1.96(1.98)2.26(2.29)1.70(1.73)

10. Interaction energies,  E, of the water molecule adsorbed on four different goethite clusters using the B3LYP/SVP approach. Energies are given in kcal/mol. Fe 4 -H 2 O (Fig. 1a)Fe 6 -H 2 O (Fig. 1c) Low-Spin-16.4Low-Spin-21.3 High-Spin-20.9High-Spin-24.6 Closed Shell a -19.2(-16.5)Closed Shell-20.1(-16.5) Fe 6 -H 2 O (Fig. 1b)Fe 8 -H 2 O (Fig. 1d) Low-Spin-18.3Low-Spin-16.8 High-Spin-21.7High-Spin-17.8 Closed Shell a -17.5(-13.2)Closed Shell-15.2(-13.1) a values in parentheses are results obtained with the SVP+sp basis set

11. 2a 2b 2c 2d

12. 1. 3a 3b 3c 3d

13. 4

14. Interaction energies,  E, of acetic acid, acetate, 2,4-D, 2,4-D – and benzene adsorbed on two goethite clusters using the closed shell B3LYP approach and two basis sets. Energies are given in kcal/mol. System Figure  E(kcal/mol) (SVP basis)  E(kcal/mol) (SVP+sp basis) Fe 4 -HAc2a-22.7-25.3 Fe 6 -HAc2b-23.7-25.0 Fe 4 -Ac –a 2c-55.4-43.4 Fe 6 - Ac – 2d-58.3-50.6 Fe 4 -2,4-D3a-20.9-21.1 Fe 6 -2,4-D3b-23.9-25.9 Fe 4 -2,4-D – 3c-38.2-32.1 Fe 6 -2,4-D – 3d-37.4-31.3 Fe 6 - C 6 H 6 4-2.6(-13.1) b -4.4 a proton transfer from the goethite surface to the Ac – anion b in parentheses single point MP2/SVP result

15. CONCLUSIONS Our investigations showed that the (110) goethite surface formed by three types of the hydroxyl groups offers a variety of possibilities for hydrogen bond formation with appropriate polar adsorbents. Two OH types, hydroxo- and µ-hydroxo, have sufficient flexibility for bending allowing them to act as proton acceptors while the third type, µ3-hydroxo, acts only as proton donor due to its more pronounced rigidity. Calculated interaction energies on different sites are ca. -20 kcal/mol for the water molecule, a number which is in line with the number and type of hydrogen bonds formed. Slightly larger interaction energies were observed for neutral acetic acid and 2,4-D in comparison to the goethite/water complexes. The aromatic ring actively participates in the interaction with the goethite surface groups. Interactions with the nonpolar, aromatic benzene molecule are much weaker. However, the estimated interaction energy range of -5 to -8 kcal/mol is still significant. This result rationalizes why goethite plays an important role for the retention of polyaromatic hydrocarbons in soils.

16. INTERACTION OF THE 2,4-DICHLOROPHENOXYACETIC ACID HERBICIDE WITH SOIL ORGANIC MATTER The term “soil organic matter” (SOM) is generally used to represent the organic constituents in the soil Humic substances (HS) are one of the major constituents of the terrestrial (SOM) and aquatic (dissolved SOM) carbon pool Humic acids - the fraction of HS that is not soluble in water under acidic conditions (pH < 2) but is soluble at higher pH values Fulvic acids - the fraction of HS that is soluble in water under all pH conditions Humin - the fraction of HS that is not soluble in water at any pH value BACKGROUND

17. STUDIED SYSTEMS + CH 3 NH 2,H2O,H2O, CH 3 COH,CH 3 COOH, CH 3 NH 3 + and Ca +2 ···CH 3 COO ‾ bridge GOAL Humic acids contain several relevant functional groups, mainly carboxyl, carbonyl, alcoholic and phenolic units, which play a major role in binding of polar molecules from a polar solvent environment. The aim of this work was to study the interactions of molecular and anionic forms of 2,4-D herbicide with these functional groups.

18. COMPUTATIONAL DETAILS: All calculations were performed at DFT level of theory with the TURBOMOLE and GAUSSIAN03 programs Density functional: B3LYP Basis Set: SVP, SVP+sp The polarizable continuum model, PCM and the conductor-like screening model, COSMO were used to computer the calculations in solution Two models were used to perform the calculation in solution: the microsolvation (g) and the global solvation (gs) and the combination of them (gsm) All results are BSSE corrected

19. RESULTS

20. Complex formation a ∆E g ∆H g ∆G g ∆E gs ∆H gs ∆G gs Me-CHO + 2,4-D → Me-CHO···2,4-D -11.4-8.61.2-2.6 0.210.0 Me-OH + 2,4-D → Me-OH···2,4-D -12.5-9.40.2-4.2 -1.14.1 Me-NH 2 + 2,4-D → Me-NH 2 ···2,4-D -13.9-11.1-2.0-7.3 -4.54.6 Me-COOH + 2,4-D → Me-COOH···2,4-D -18.0-15.1-4.0-1.6 1.312.4 (H 2 O) 2 + 2,4-D → 2H 2 O···2,4-D -18.8-15.2-2.5-4.0 -0.412.3 Me-NH 3 + + 2,4-D → Me-NH 3 + ···2,4-D -33.2-29.6-18.9-4.9 -1.39.4  H gs =  H g -  E g +  E gs  G gs =  G g -  E g +  E gs MS + 2,4–D → MS···2,4–D MS + 2,4–D – → MS···2,4–D – Interaction energies, enthalpies and Gibbs free energies for complexes of 2,4 ‑ D and selected MS and water molecules. All calculations were performed at the B3LYP/SVP+sp level of theory. Energies are BSSE corrected a and given in kcal/mol. Subscript “g” denotes the gas phase calculations. Subscript “gs” denotes the results obtained with the global solvation approach (PCM calculations)

21. microsolvationglobal solvation + microsolvation Model reaction a ∆E g ∆H g ∆G g ∆E gsm ∆H gsm ∆G gsm Me-CHO···2H 2 O + 2,4-D···2H 2 O → Me-CHO···2,4-D + (H 2 O) 4 -2.2-1.8-1.5-4.1-3.7-3.4 Me-OH···2H 2 O + 2,4-D···2H 2 O → Me-OH···2,4-D + (H 2 O) 4 -3.9-3.6-4.3-8.9-8.6-9.3 Me-NH 2 ···2H 2 O + 2,4-D ···2H 2 O → Me-NH 2 ···2,4-D + (H 2 O) 4 -3.1 -3.8-4.7 -5.4 Me-NH 3 + ···2H 2 O + 2,4-D ···2H 2 O → Me-NH 3 + ··2,4-D + (H 2 O) 4 -2.8-2.20.9-0.6-0.13.0 Me-COOH ···2H 2 O + 2,4-D···2H 2 → Me-COOH···2,4-D + (H 2 O) 4 -0.8 -1.5 -0.2 -0.9 a – Me = -CH 3 MS···2H 2 O + 2,4-D···2H 2 O → MS···2,4-D + (H 2 O) 4 Energies, enthalpies and Gibbs free energies of reactions between the 2,4–D···2H 2 O complex and MS···2H 2 O complexes for the microsolvation and combined micro- and global solvation approaches. All calculations were performed at the B3LYP/SVP+sp level of theory. Energies are given in kcal/mol. Subscript “gsm” denotes the results obtained with combined approach.

23. Complex formation a ∆E g ∆H g ∆G g ∆E gs ∆H gs ∆G gs Me-CHO + 2,4-D – → Me-CHO····2,4-D – -11.5-9.4-1.31.4 3.511.6 Me-OH + 2,4-D – → Me-OH····2,4-D – -15.3-13.0-4.4-1.6 0.79.3 Me-NH 2 + 2,4-D – → Me-NH 2 ····2,4-D – -8.2-6.11.62.1 4.211.9 Me-COOH + 2,4-D – → Me-COOH····2,4-D – -21.2-19.6-8.6-2.4 -0.810.2 2H 2 O + 2,4-D – → 2H 2 O····2,4-D – -26.7-24.0-12.4-3.8 -1.110.5 Me-NH 3 + + 2,4-D – → Me-NH 3 + ···2,4-D – -116.0-115.8-106.6-0.6 -0.58.8 “Subscript “g” denotes the gas phase calculations. Subscript gs” denotes the results obtained with the global solvation approach (PCM calculations). Interaction energies, enthalpies and Gibbs free energies for complexes of 2,4 ‑ D– anion and selected MS and water molecules. All calculations were performed at the B3LYP/SVP+sp level of theory. Energies are BSSE correcteda and given in kcal/mol. a – Me = -CH 3

24. microsolvationglobal solvation + microsolvation Model reaction a ∆E g ∆H g ∆G g ∆E gsm ∆H gsm ∆G gsm Me-CHO···2H 2 O + 2,4-D – ···2H 2 O → Me-CHO···2,4-D‾ + (H 2 O) 4 5.75.35.1-1.1-1.5-1.7 Me-OH···2H 2 O + 2,4-D – ···2H 2 O → Me-OH···2,4-D – + (H 2 O) 4 1.20.80.1-7.4-7.8-8.5 Me-NH 2 ···2H 2 O + 2,4-D – ···2H 2 O → Me-NH 2 ···2,4-D – + (H 2 O) 4 10.510.29.24.13.82.8 Me-NH 3 + ···2H 2 O + 2,4-D – ···2H 2 O → Me-NH 3 + ···2,4-D‾ + (H 2 O) 4 -88.3-89.2-86.53.12.24.9 Me-COOH ···2H 2 O + 2,4-D – ···2H 2 O → Me-COOH···2,4-D – + (H 2 O) 4 3.92.52.8-2.3-3.7-3.4 a – Me= -CH 3 ; Subscript “gsm” denotes the results oobtained with combined approach. Energies are given in kcal/mol. Ca 2+ (H 2 O) 6 +2,4-D – ···2H 2 O + Ac‾ ···2H 2 O → -220.9 -221.0 -216.3 -11.5 -11.6 -6.6 2,4-D‾···Ca 2+ (H 2 O) 2 ···Ac‾+2(H 2 O) 4 Energies, enthalpies, enthalpies and Gibbs free energies of reactions between the 2,4-D‾···2H 2 O complex and MS···2H 2 O complexes for the microsolvation and combined micro- and global solvation approaches. All calculations were performed at the B3LYP/SVP+sp level of theory.

26. CONCLUSIONS: It has been shown that the consideration of this combined solvation model is crucial for the evaluation of chemical reaction energies; The application of the exchange reaction showed that the neutral 2,4-D molecule is able to form stable complexes in a polar solvent environment with a large variety of functional groups; On the other hand, the anionic form of 2,4-D is found to form stable complexes in a polar solvent like the soil solution only with hydroxyl and carboxyl functional groups; In general, the interactions of solvated ionic species are very stable in the gas phase and in the microsolvation model; Continuum solvation has a destabilizing effect due to a preferred solvation of the individual charged reactants as compared to the neutral or charged complexes; The cation bridge, which is by far the most important interaction mechanism in soil, has been found to be very stable with a final  G value of -6.6 kcal/mol taking Ca 2+ as example.

27. Acknowledgments Austrian Science Fund