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Boily, Jean-FrancoisORCID iD iconorcid.org/0000-0003-4954-6461
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Publications (10 of 92) Show all publications
Lindholm, J., Boily, J.-F. & Holmboe, M. (2019). Deconvolution of Smectite Hydration Isotherms. ACS Earch and Space Chemistry, 3(11), 2490-2498
Open this publication in new window or tab >>Deconvolution of Smectite Hydration Isotherms
2019 (English)In: ACS Earch and Space Chemistry, ISSN 2472-3452, Vol. 3, no 11, p. 2490-2498Article in journal (Refereed) Published
Abstract [en]

Sorption isotherm models have traditionally served as an invaluable tool to characterize synthesized and natural mineral particles. However, for particles susceptible to substantial hydration, such as the swelling smectite clay minerals and other layered minerals displaying intercalation of discrete water monolayers, traditional isotherm models inadequately describe the total water uptake as a result of the change in available surface sites and area during the hydration process. With the goal of deconvoluting the water uptake behavior of swelling smectite minerals, this research presents a novel composite isotherm model that describes water uptake by surface adsorption, condensation, and stepwise intercalation. A set of eight montmorillonite samples ion-exchanged with different countercations (Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, and Cu2+) were used to develop this model, which was based on gravimetric uptake measurements and X-ray diffraction data of basal spacings obtained from relative humidity conditions up to 98% relative humidity.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
water vapor, clays, montmorillonite, adsorption, ion hydration, XRD
National Category
Materials Chemistry
Identifiers
urn:nbn:se:umu:diva-166800 (URN)10.1021/acsearthspacechem.9b00178 (DOI)000499739500014 ()
Funder
The Kempe FoundationsSwedish Research Council, 2016-03808
Available from: 2020-01-03 Created: 2020-01-03 Last updated: 2020-01-03Bibliographically approved
Boily, J.-F., Fu, L., Tuladhar, A., Lu, Z., Legg, B. A., Wang, Z. M. & Wang, H. (2019). Hydrogen bonding and molecular orientations across thin water films on sapphire. Journal of Colloid and Interface Science, 555, 810-817
Open this publication in new window or tab >>Hydrogen bonding and molecular orientations across thin water films on sapphire
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2019 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 555, p. 810-817Article in journal (Refereed) Published
Abstract [en]

Hypothesis: Water vapor binding to metal oxide surfaces produces thin water films with properties controlled by interactions with surface hydroxo sites. Hydrogen bonding populations vary across films and induce different molecular orientations than at the surface of liquid water. Identifying these differences can open possibilities for tailoring film-mediated catalytic reactions by choice of the supporting metal oxide substrate.

Experiments: The (0001) face of a single sapphire (α-Al2O3) sample exposed to water vapor and the surface of liquid water were probed by polarization dependent Sum Frequency Generation-Vibration Spectroscopy (SFG-VS). Molecular dynamics (MD) provided insight into the hydrogen bond populations and molecular orientations across films and liquid water.

Findings: SFG-VS revealed a submonolayer film on sapphire exposed to 43% relative humidity (R.H.), and a multilayer film at 78% R.H. Polarization dependent SFG-VS spectra showed that median tilt angles of free OH bonds on the top of films are at ∼43° from the normal of the (0001) face but at 38° on neat liquid water. These values align with MD simulations, which also show that up to 36% of all OH bonds on films are free. This offers new means for understanding how interfacial reactions on sapphire-supported water films could contrast with those involving liquid water.

Place, publisher, year, edition, pages
Elsevier, 2019
Keywords
Sapphire, Water, Film, Sum frequency generation, Molecular dynamics, Spectroscopy, Hydration, Atmosphere
National Category
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-164970 (URN)10.1016/j.jcis.2019.08.028 (DOI)000488652300081 ()31425917 (PubMedID)
Funder
Swedish Research Council, VR 2016-03808Carl Tryggers foundation The Kempe Foundations, 130367
Available from: 2019-11-12 Created: 2019-11-12 Last updated: 2019-11-12Bibliographically approved
Henriksson, N., Marshall, J., Lundholm, J., Boily, A., Boily, J.-F. & Nasholm, T. (2019). Improved in vivo measurement of alternative oxidase respiration in field-collected pine roots. Physiologia Plantarum: An International Journal for Plant Biology, 167(1), 34-47
Open this publication in new window or tab >>Improved in vivo measurement of alternative oxidase respiration in field-collected pine roots
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2019 (English)In: Physiologia Plantarum: An International Journal for Plant Biology, ISSN 0031-9317, E-ISSN 1399-3054, Vol. 167, no 1, p. 34-47Article in journal (Refereed) Published
Abstract [en]

Cellular respiration via the alternative oxidase pathway (AOP) leads to a considerable loss in efficiency. Compared to the cytochrome pathway (COP), AOP produces 0-50% as much ATP per carbon (C) respired. Relative partitioning between the pathways can be measured in vivo based on their differing isotopic discriminations against O-18 in O-2. Starting from published methods, we have refined and tested a new protocol to improve measurement precision and efficiency. The refinements detect an effect of tissue water content (P < 0.0001), which we have removed, and yield precise discrimination endpoints in the presence of pathway-specific respiratory inhibitors [CN- and salicylhydroxamic acid (SHAM)], which improves estimates of AOP/COP partitioning. Fresh roots of Pinus sylvestris were sealed in vials with a CO2 trap. The air was replaced to ensure identical starting conditions. Headspace air was repeatedly sampled and isotopically analyzed using isotope-ratio mass spectrometry. The method allows high-precision measurement of the discrimination against O-18 in O-2 because of repeated measurements of the same incubation vial. COP and AOP respiration discriminated against O-18 by 15.1 +/- 0.3 parts per thousand and 23.8 +/- 0.4 parts per thousand, respectively. AOP contributed to root respiration by 23 +/- 0.2% of the total in an unfertilized stand. In a second, nitrogen-fertilized, stand AOP contribution was only 14 +/- 0.2% of the total. These results suggest the improved method can be used to assess the relative importance of COP and AOP activities in ecosystems, potentially yielding information on the role of each pathway for the carbon use efficiency of organisms.

National Category
Environmental Sciences
Identifiers
urn:nbn:se:umu:diva-162659 (URN)10.1111/ppl.12910 (DOI)000478917400004 ()30561048 (PubMedID)
Projects
Bio4Energy
Available from: 2019-09-05 Created: 2019-09-05 Last updated: 2019-09-06Bibliographically approved
Wang, X., Phillips, B. L., Boily, J.-F., Hu, Y., Hu, Z., Yang, P., . . . Zhu, M. (2019). Phosphate Sorption Speciation and Precipitation Mechanisms on Amorphous Aluminum Hydroxide. Soil Systems, 3(1), Article ID 20.
Open this publication in new window or tab >>Phosphate Sorption Speciation and Precipitation Mechanisms on Amorphous Aluminum Hydroxide
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2019 (English)In: Soil Systems, ISSN 2571-8789, Vol. 3, no 1, article id 20Article in journal (Refereed) Published
Abstract [en]

Aluminum (Al) oxides are important adsorbents for phosphate in soils and sediments, and significantly limit Phosphate (P) mobility and bioavailability, but the speciation of surface-adsorbed phosphate on Al oxides remains poorly understood. Here, phosphate sorption speciation on amorphous Al hydroxide (AAH) was determined under pH 3-8 and P concentration of 0.03 mM-15 mM using various spectroscopic approaches, and phosphate precipitation mechanisms were discussed as well. AAH exhibits an extremely high phosphate sorption capacity, increasing from 3.80 mmol/g at pH 7 to 4.63 mmol/g at pH 3. Regardless of reaction pH, with increasing P sorption loading, the sorption mechanism transits from bidentate binuclear (BB) surface complexation with d(P-Al) of 3.12 angstrom to surface precipitation of analogous amorphous AlPO4 (AAP), possibly with ternary complexes, such as (equivalent to Al-O)(2)-PO2-Al, as intermediate products. Additionally, the percentage of precipitated phosphate occurring in AAP linearly and positively correlates with P sorption loading. Compared to phosphate reaction with ferrihydrite, phosphate adsorbs and precipitates more readily on AAH due to the higher solubility product (K-sp) of AAH. The formation of AAP particles involves Al-III release, which is promoted by phosphate adsorption, and its subsequent precipitation with phosphate at AAH surfaces or in the bulk solution.

Place, publisher, year, edition, pages
MDPI, 2019
Keywords
phosphate, speciation, sorption, precipitation, Al hydroxide
National Category
Geochemistry
Identifiers
urn:nbn:se:umu:diva-166833 (URN)10.3390/soilsystems3010020 (DOI)000500757400019 ()
Funder
Swedish Research Council, 2016-03808
Available from: 2020-01-03 Created: 2020-01-03 Last updated: 2020-01-03Bibliographically approved
Yeşilbaş, M., Holmboe, M. & Boily, J.-F. (2019). Residence times of nanoconfined CO2 in layered aluminosilicates. Environmental Science: Nano, 6(1), 146-151
Open this publication in new window or tab >>Residence times of nanoconfined CO2 in layered aluminosilicates
2019 (English)In: Environmental Science: Nano, ISSN 2051-8153, Vol. 6, no 1, p. 146-151Article in journal (Refereed) Published
Abstract [en]

Nanoconfinement of CO2 in layered aluminosilicates contributes to the capture and release of this greenhouse gas in soils. In this work, we show that the residence times of CO2 in montmorillonite are lowered by 15 min for each 1 degrees C increment in temperature during venting. Molecular simulations showed that activation energies of release are no more than half of the experimentally derived value of 34 kJ mol(-1). This raised the possibility of additional processes limiting CO2 mobility in real materials, including (chemi)sorption at reactive sites or frayed edges or defects. The residence times (approximate to 1616 min at -50 degrees C to approximate to 6 min at 60 degrees C) for some of the driest (approximate to 1.4 mmol H2O per g) montmorillonites that can be produced at ambient temperatures are readily lowered by inclusion of additional water. They are, in turn, prolonged again as the water content and interlayer spacing become smaller through venting. These efforts showed that soil-building clay minerals will lose their propensity to dynamically exchange CO2 as temperatures continue to rise, yet they may retain CO2 more efficiently in cold seasons as soils will become depleted in moisture content.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Environmental Sciences Geochemistry
Identifiers
urn:nbn:se:umu:diva-157978 (URN)10.1039/c8en01156g (DOI)000461698700010 ()
Available from: 2019-04-10 Created: 2019-04-10 Last updated: 2019-04-10Bibliographically approved
Zhou, L., Martin, S., Cheng, W., Lassabatere, L., Boily, J.-F. & Hanna, K. (2019). Water Flow Variability Affects Adsorption and Oxidation of Ciprofloxacin onto Hematite. Environmental Science and Technology, 53(17), 10102-10109
Open this publication in new window or tab >>Water Flow Variability Affects Adsorption and Oxidation of Ciprofloxacin onto Hematite
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2019 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 53, no 17, p. 10102-10109Article in journal (Refereed) Published
Abstract [en]

The mobility of pharmaceuticals in environmental systems is under great scrutiny in the scientific literature and in the press. Still, very few reports have focused on redox-driven transformations when these compounds are bound to mineral surfaces, and how their transport is affected under flow-through conditions. In this study, we examined the adsorption and electron transfer reactions of ciprofloxacin (CIP) in a dynamic column containing nanosized hematite (α-Fe2O3). CIP binding and the subsequent redox transformation were strongly dependent on inflow pH and residence time. These reactions could be predicted using transport models that account for adsorption and transformation kinetics. Our results show that flow interruption over a 16 h period triggers oxidation of hematite-bound CIP into byproducts. These reactions are likely facilitated by inner-sphere iron–CIP complexes formed via the sluggish conversion from outer-sphere complexes during interrupted flow. When intermittent flow/no-flow conditions were applied sequentially, a second byproduct was detected in the column effluent. This work sheds light on a much overseen aspect of redox transformations of antibiotics under flow-through conditions. It has important implications in adequately predicting transport, and in developing risk assessments of these emerging compounds in the environment.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Environmental Sciences
Identifiers
urn:nbn:se:umu:diva-164628 (URN)10.1021/acs.est.9b03214 (DOI)000484644500013 ()31408603 (PubMedID)2-s2.0-85071786699 (Scopus ID)
Available from: 2019-11-08 Created: 2019-11-08 Last updated: 2019-11-08Bibliographically approved
Cheng, W., Hanna, K. & Boily, J.-F. (2019). Water Vapor Binding on Organic Matter-Coated Minerals. Environmental Science & Technology, 53(3), 1252-1257
Open this publication in new window or tab >>Water Vapor Binding on Organic Matter-Coated Minerals
2019 (English)In: Environmental Science & Technology, ISSN 0013-936X, Vol. 53, no 3, p. 1252-1257Article in journal (Refereed) Published
Abstract [en]

Atmospheric water vapor binding to soils is a key process driving water availability in unsaturated terrestrial environments. Using a representative hydrophilic iron oxyhydroxide, this study highlights key mechanisms through which water vapor (i) adsorbs and (ii) condenses at mineral surfaces coated with Leonardite humic acid (LHA). Microgravimetry and vibrational spectroscopy showed that liquid-like water forms in the three-dimensional array of mineral-bound LHA when present at total C/Fe ratios well exceeding similar to 73 mg C per g Fe (26 C atoms/nm(2)). Below these loadings, minerals become even less hydrophilic than in the absence of LHA. This lowering in hydrophilicity is caused by the complexation of LHA water-binding sites to mineral surfaces, and possibly by conformational changes in LHA structure removing available condensation environments for water. An empirical relationship predicting the dependence of water adsorption densities on LHA loadings was developed from these results. Together with the molecular-level description provided in this work, this relationship should guide efforts in predicting water availability, and thereby occurrences of water-driven geochemical processes in terrestrial environments.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Environmental Sciences
Identifiers
urn:nbn:se:umu:diva-156878 (URN)10.1021/acs.est.8b05134 (DOI)000458220600022 ()30608658 (PubMedID)
Available from: 2019-03-11 Created: 2019-03-11 Last updated: 2019-03-11Bibliographically approved
Yu, C., Boily, J.-F., Shchukarev, A., Drake, H., Song, Z., Hogmalm, K. J. & Åström, M. E. (2018). A cryogenic XPS study of Ce fixation on nanosized manganite and vernadite: Interfacial reactions and effects of fulvic acid complexation. Chemical Geology, 483, 304-311
Open this publication in new window or tab >>A cryogenic XPS study of Ce fixation on nanosized manganite and vernadite: Interfacial reactions and effects of fulvic acid complexation
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2018 (English)In: Chemical Geology, ISSN 0009-2541, E-ISSN 1872-6836, Vol. 483, p. 304-311Article in journal (Refereed) Published
Abstract [en]

This study investigated interfacial reactions between aqueous Ce(III) and two synthetic nanosized Mn (hydr-)oxides (manganite: γ-MnOOH, and vernadite: δ-MnO2) in the absence and presence of Nordic Lake fulvic acid (NLFA) at circumneutral pH by batch experiments and cryogenic X-ray photoelectron spectroscopy (XPS). The surfaces of manganite and vernadite were negatively charged (XPS-derived loadings of (Na + K)/Cl > 1) and loaded with 0.42–4.33 Ce ions nm−2. Manganite stabilized Ce-oxidation states almost identical to those for vernadite (approximately 75% Ce(IV) and 25% Ce(III)), providing the first experimental evidence that also a Mn(III) phase (manganite) can act as an important scavenger for Ce(IV) and thus, contribute to the decoupling of Ce from its neighboring rare earth elements and the development of Ce anomaly. In contrast, when exposed to Ce(III)-NLFA complexes, the oxidation of Ce by these two Mn (hydr-)oxides was strongly suppressed, suggesting that the formation of Ce(III) complexes with fulvic acid can stabilize Ce(III) even in the presence of oxidative Mn-oxide surfaces. The experiments also showed that Ce(III) complexed with excess NLFA was nearly completely removed, pointing to a strong preferential sorption of Ce(III)-complexed NLFA over free NLFA. This finding suggests that the Ce(III)-NLFA complexes were most likely sorbed by their cation side, i.e. Ce(III) bridging between oxide groups on the Mn (hydr-)oxides and negatively-charged functional groups in NLFA. Hence, Ce(III) was in direct contact with the oxidative manganite and vernadite but despite that not oxidized. An implication is that in organic-rich environments there may be an absence of Ce(IV) and Ce anomaly despite otherwise favorable conditions for Ce(III) oxidation.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Cryogenic XPS, Manganite, Vernadite, Oxidative scavenging, Ce anomaly
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:umu:diva-146721 (URN)10.1016/j.chemgeo.2018.02.033 (DOI)000429492300027 ()2-s2.0-85042905870 (Scopus ID)
Available from: 2018-04-18 Created: 2018-04-18 Last updated: 2018-06-13Bibliographically approved
Wang, X., Kubicki, J. D., Boily, J.-F., Waychunas, G. A., Hu, Y., Feng, X. & Zhu, M. (2018). Binding geometries of silicate species on ferrihydrite surfaces. ACS EARTH AND SPACE CHEMISTRY, 2(2), 125-134
Open this publication in new window or tab >>Binding geometries of silicate species on ferrihydrite surfaces
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2018 (English)In: ACS EARTH AND SPACE CHEMISTRY, ISSN 2472-3452, Vol. 2, no 2, p. 125-134Article in journal (Refereed) Published
Abstract [en]

Silicate sorption on ferrihydrite surfaces, as monomers, oligomers, and polymers, strongly affects ferrihydrite crystallinity, thermodynamic stability, and surface reactivity. How these silicate species bind on ferrihydrite surfaces is, however, not well understood. We have determined silicate binding geometries using a combination of X-ray absorption spectroscopy (XAS), differential atomic pair distribution function (d-PDF) analysis, and density functional theory (DFT) calculations. Silicon K-edge absorption pre edges and DFT-predicted energies indicate that silicate forms monomeric monodentate mononuclear (MM) complexes at low silicate sorption loadings. With increasing silicate loading, the pre-edge peak shifts to higher energies, suggesting changes in the silicate binding geometry toward multidentate complexation. The d-PDF analysis determines the Si Fe interatomic distance to be 3.25 A for the high-loading samples. The DFT calculations indicate that such distance corresponds to an oligomer in the bidentate binuclear (BB) binding geometry. The transition of the silicate sorption geometry accompanied by polymerization can affect stability of ferrihydrite and its adsorption and redox reactivity and increase the degree of Si isotopic fractionation upon silicate sorption on Fe oxides. MM monomeric complexes and BB oligomeric complexes should be used for surface complexation models predicting silicate sorption on Fe oxide surfaces.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2018
Keywords
silicate, ferrihydrite, binding geometry, polymerization, Si K-edge LINES spectroscopy, differential PDF alysis, DFT calculations
National Category
Materials Chemistry
Identifiers
urn:nbn:se:umu:diva-145786 (URN)10.1021/acsearthspacechem.7b00109 (DOI)000425569600006 ()
Available from: 2018-03-22 Created: 2018-03-22 Last updated: 2018-06-09Bibliographically approved
Yeşilbaş, M., Holmboe, M. & Boily, J.-F. (2018). Cohesive vibrational and structural depiction of intercalated water in montmorillonite. ACS Earth and Space Chemistry, 2(1), 38-47
Open this publication in new window or tab >>Cohesive vibrational and structural depiction of intercalated water in montmorillonite
2018 (English)In: ACS Earth and Space Chemistry, E-ISSN 2472-3452, Vol. 2, no 1, p. 38-47Article in journal (Refereed) Published
Abstract [en]

The vibrational spectral profiles of Na- and Ca-montmorillonite (MMT) of controlled water layer populations (nW) was extracted by chemometric analysis of new Fourier transform infrared (FTIR) spectroscopy data and validated by mixed-layer modeling of previously published X-ray diffraction data. These efforts resolved FTIR spectral profiles of 0W, 1W, and 2W interlayers, which can now be used to explore the distinct hydration states of MMT. These spectral profiles reflect water populations organized around interlayer cations (Na+, Ca2+), interacting with siloxane groups of the basal face of the interlayer, and with other bound and “free” water molecules. This cohesive description of water-bearing clays provides the link needed to relate vibrational to structural attributes of these geochemically important materials.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
Keywords
adsorption, montmorillonite, vibration spectroscopy, water vapor, X-ray diffraction
National Category
Geochemistry
Identifiers
urn:nbn:se:umu:diva-143020 (URN)10.1021/acsearthspacechem.7b00103 (DOI)000423141600005 ()
Available from: 2017-12-14 Created: 2017-12-14 Last updated: 2018-06-09Bibliographically approved
Projects
Molecular Controls of Mineral-CO2 Interactions [2009-03110_VR]; Umeå UniversityMineral Surface Structural Controls on Gas-Phase Adsorption Reactions [2012-02976_VR]; Umeå UniversityChemistry within the confines of mineral-bound thin water films [2016-03808_VR]; Umeå University
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ORCID iD: ORCID iD iconorcid.org/0000-0003-4954-6461

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