Environmental Colloids and Nanoparticles: Occurrence, Behaviour and Relevance for Engineered Particles

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Nanogeosciences Environmental Colloids and

for Engineered Particles FRANK VON DER KAMMER *

PLATHE HOFMANN *,1 * MIKE KELLY HOCHELLA PLATHE *,1

LEGROS NEUBAUER * * PHILIPPE ELISABETH LE COUSTUMER

of Vienna 1 Virginia * University Techof Vienna 2

1 Nanogeosciences Environmental Colloids and Nanoparticles: Occurrence, Behaviour and Relevance for Engineered Particles FRANK VON DER KAMMER * THILO FRANK HOFMANN VON DER * KAMMER * KELLY THILO PLATHE HOFMANN *,1 * MIKE KELLY HOCHELLA PLATHE *,1 1 SAMUEL MIKE HOCHELLA LEGROS * 1 ELISABETH SAMUEL LEGROS NEUBAUER * * PHILIPPE ELISABETH LE COUSTUMER NEUBAUER * 2 PHILIPPE LE COUSTUMER 2 * University of Vienna 1 Virginia * University Techof Vienna 2 University 1 Virginia Tech of Bordeaux SDS. % 2 University of Bordeaux

2 Overview Introduction Trace metal associations with mineral colloids Trace metal associations with mineral colloids & natural organic matter Contaminant transport with natural and engineered nanoparticles

3 natural colloids, engineered & environmental nanoparticles

4 what are environmental aquatic colloids? environmental aquatic colloids natural colloids anthropogenic colloids engineered nanoparticles origin inorganic colloids organic colloids wear & corrosion products standard industrial products - silicates (e.g. clays) -macromolecules - from tire & brakes -polymers smectites montmorillonite nontronite hectorite humic acids fulvic acids polysaccharides - from catalysts (e.g. Pt, Pd) - metals (wear in bearings) - metal oxides (roof run-off) - surfactants - dyes & pigments - metal oxides chlorites proteins - additives to lubricants NP metals & metal oxides mica kaolinite peptides exo-polymers, EPS waste & combustion products - metals (Au, Ag, Fe) - metal oxides (of Ti, Zn, Zr, Ce ) composition - oxides / hydroxides - bio- colloids -soot - metal tubes and wires Fe-oxohydroxides bacteria - anthropogenic humic acids carbon based Mn-oxides viruses from e.g. waste dumps - fullerenes - carbonates fungi - tar leachates in plumes - single & multi walled nanotubes - phospates - coal/soot/black carbon -fly ash hybride structures - metal sulfides - cellular debris - fine dust (inorganic & organic) - quantum dots - polym. silicic acid - functionalized materials - core-shell structures Christian, v.d.kammer, Baalousha, Hofmann (28)

5 environmental aquatic colloids TEM: polystyrene-latex TEM: soil colloids municipal road run-off 1nm REM: soil colloids TEM: synth. hematite soil colloids attached to larger grains TEM: synth. modified hematite TEM: synth. akaganeite

6 what are environmental aquatic colloids? A) Spores covered and glued together by iron oxyhydroxide globules B) Clay and iron oxyhydroxide globules, aggregated by a mesh of organic filaments C) Si-rich colloids aggregated in looser matrix of organic material Buffle & Leppard 199 EST Stained Pb(II) D) Inorganic colloids bound by fibrillar material E) Soil-derived fulvic compounds aggregated in slightly larger entities Stained UO2+ Stained Pb(II)

7 Reactions Important reactions of environmental nanoparticles - transport (mobilization attachment) - formation, transformation and dissolution - growth, aggregation seggregation - interaction with contaminants, nutrients and NOM (co-transport) -electrontransfer

8 colloid dynamics in groundwater translocation leakage from vadoze zone ground/seapage water dissolution mobilization ionic strength ph valence of ions dissolution of cements hydraulic effects / diffusion Eh I s ph Ca ++ Na + deposition stabilization transport generation second. mineral formation precipitation biological growth Eh ph filtration 8

9 Biogenic Uraninite nanoparticles Biogenic Uraninite nanoparticles formed under anoxic conditions by Shewanella oneidensis strain MR-1, showing UO 2 lattice fringes. John R. Bargar, Rizlan Bernier-Latmani, Daniel E. Giammar and Bradley M. Tebo (Elements 28)

10 Cu-nanoparticles formed under anoxic conditions (floodplain soil) Frank-Andreas Weber, Andreas Voegelin, Ralf Kaegi and Ruben Kretzschmar (Nature 29)

11 Self-assembly of nanoparticles: a pure nanotechnology invention? Markus Niederberger and Helmut Cölfen (PCCP 26)

12 oriented attachment of anatase nanoparticles (hydrothermal coarsening) R. LEE PENN and JILLIAN F. BANFIELD (GCA 1999) how to distinguish aggregate (strong bonds) and agglomerate (weak bonds)

13 oriented aggregation and transformation of ferrihydrite particles to goethite how to distinguish aggregate (strong bonds) and agglomerate (weak bonds) Virany M. Yuwono, Nathan D. Burrows, Jennifer A. Soltis and R. Lee Penn (JACS 21)

14 Overview Trace metal associations with mineral colloids Trace metal associations with mineral colloids & natural organic matter Contaminant transport with natural and engineered nanoparticles

15 Plathe; von der Kammer; Hochella et al. 21 (Environmetnal Chemistry)

16 Ti 4 counts Si Fe Ni brookite TiO 2 Ti 1 Al Zr Fe Ni Zn energy (kev) 1 Pb Zr nm 2 nm

17 Al Si Ca Fe Ni 4 Mg Ce allanite counts (Ca,Ce)(Al,Fe)[O OH SiO 4 Si 2 O 7 ] Ce 1 Th Ca La Ce La Fe Ni Zn Pb Th energy (kev) nm 2 nm

18 Overview Trace metal associations with mineral colloids Trace metal associations with mineral colloids & natural organic matter Contaminant transport with natural and engineered nanoparticles

19 FlowFFF Analysis of soil NOM ph9 - organic rich top-soil extraction extraction clean-up dry sieving < 12 µm precipitate: HA washing s/l ratio 1/1 overhead shaker 1. MQ water neutralization / dissolution dissolve precipitate at ph 7 (+NaOH) 2. NaCl.1 mol L * MQ water 4. HCl ph 1. 2 * MQ water (24h each) dialysis dialysis in 1, MWCO tubes until AgNO 3 test negative separation at 32 rcf for 6 min. after each step HA extract: MOC extraction at ph 9 centrifugation at 32 rcf for 24 h 3 times at ph 9 (NaOH; 24h) separation at 32 rcf for 12 min. supernatant: low-flow constant-pressure filtration over.2 µm PES acidification MOC extract to ph 1 (HCl) separation at 32 rct for 12 min. centrifugate: HA freeze drying wet storage supernatant: FA neutralization to ph 7 characterization experiments absorbtion 27 nm & fluorescence 3/ nm in a.u UV max = 3, g mol FL max = 1,7 g mol UV/VIS 1 2 fluorescence molecular weight in g mol -1 Composition of the aqueous soil extract: Cd Cu Pb Zn Fe Al Na Ca Mg Mn µg/l µg/l µg/l µg/l mg/l mg/l mg/l mg/l mg/l mg/l <, DOC C H N S O RES PO 4 F - - NO 3 NO 2 - mg/l % % % % % % mg/l mg/l mg/l mg/l mg/l ,3 <, <,3 <,2 1,3 Cl -

20 FlowFFF Analysis of original soil NOM 1 7 UV/VIS (a.u.) & Ti (µg L -1 ) 1 Al Ti UV/VIS 26 nm ~ size distribution Fe UV 27 nm Al Fe Ti 1 1 Al (µg L -1 ) Fe (µg L -1 ) 3 domains fluorescing NOM (~ 1 nm) UV absorbing NOM (1. 4 nm) particulates (from 3 nm) selective or predominant metal binding to a domain UV/VIS (a.u.) Cu Bi hydrodynamic radius (nm) Pb UV/VIS 26 nm ~ size distribution UV org Pb Bi Cu Pb (µg L -1 ) Bi (µg L -1 ) Cu (µg L -1 ) domain 1+2: Cu, Sb domain 2: Al, Ca, Zn, Ni, U, Pt, Cd, Cr, Co domain 2 & 3: Fe, Mn, P Pb, Ti, Bi, Sn, V hydrodynamic radius (nm) v.d.kammer & Hassellov 21 in prep.

21 FlowFFF Analysis of original soil NOM 1 7 UV/VIS (a.u.) & Ti (µg L -1 ) 1 organic (NOM) Al Ti Fe solid mineral UV 27 nm Al Fe Ti 1 1 Al (µg L -1 ) Fe (µg L -1 ) 3 domains fluorescing NOM (~ 1 nm) UV absorbing NOM (1. 4 nm) particulates (from 3 nm) selective or predominant metal binding to a domain hydrodynamic radius (nm) domain 1+2: Cu, Sb UV/VIS (a.u.) 1 Cu organic (NOM) Bi Pb solid mineral UV org Pb Bi Cu Pb (µg L -1 ) Bi (µg L -1 ) Cu (µg L -1 ) domain 2: Al, Ca, Zn, Ni, U, Pt, Cd, Cr, Co domain 2 & 3: Fe, Mn, P Pb, Ti, Bi, Sn, V hydrodynamic radius (nm) v.d.kammer & Hassellov 21 in prep.

22 HR TEM micrographs: evidence for non-humic binding phases Identified by EDX: Fe, Cu, Ti, Al, Mg, Na 2 nm 2 nm HR TEM by Philippe Le Coustumer, Bordeaux

23 FlowFFF Analysis of original & chelex treated soil NOM 1 Al 1 1 Cu 2 Abs. (a.u.) 1 1 Al (µg L -1 ) Abs. (a.u.) Cu (µg L -1 ) Abs. (a.u.) 1 Fe Fe (µg L -1 ) Abs. (a.u.) 1 Zn Zn (µg L -1 ) particle radius (nm) particle radius (nm) Original sample: shaking 6 days as is Chelex sample: shaking 6 days with 2 g Chelex /2mL of sample

24 FlowFFF Analysis of original & chelex treated soil NOM Abs. (a.u.) 1 1 Pb Pb (µg L -1 ) Abs. (a.u.) 1 1 Ti Ti (µg L -1 ) Abs. (a.u.) 1 Bi,1, Bi (µg L -1 ) Abs. (a.u.) 1 Pt,4,2 Pt (µg L -1 ), , particle radius (nm) particle radius (nm) Original sample: shaking 6 days as is Chelex sample: shaking 6 days with 2 g Chelex /2mL of sample

25 Overview Trace metal associations with mineral colloids Trace metal associations with mineral colloids & natural organic matter Contaminant transport with natural and engineered nanoparticles

26 Subsurface transport: nanoparticles as carriers for HOC particle loading transport & desorption straining filtration aggregation & straining filtration nanoparticle transport dissolution A B transport deposition aggregation & transport B 1 % transport no deposition no filtration no dissolution worst case scenario Hofmann & v.d. Kammer 29

27 Subsurface transport: nanoparticles as carriers for HOC HOC co-transport with desorption coupled desorption HOC loading on nanoparticles HOC co-transport with no/slow desorption de-coupled no desorption HOC loading on nanoparticles Equilibrium: HOC desorption is fast compared to the transport time scale HOC will partition to matrix De-coupled: HOC desorption is slow compared to the transport time scale HOC will be relocated with nanoparticles Hofmann & v.d. Kammer 29

28 Is the transport of the particles realistic? Conditions: avg. particle size 2 µm avg. pore size 1 µm porosity 3% GW renewal 3 mm/h attachment efficiency = 1-4 Kd of contaminant = groundwater radius 1-8 m (1 nm) 1-7 m (1 nm) 1 m diffusion coefficient 2.1 x 1-11 m² s x 1-12 m² s -1 Brownian displacement 39 µm h µm h -1 settling rate (D2.6).8 µm h -1 8 µm h -1 steady state, saturated, non-transient conditions 1 nm diameter particles travel time: ~1 year collisions through diffusion: ~4/h 3 per year attachment through diffusional movement particles will be lost 3. times during transport 1 nm particles travel time: ~1 year diffusion negligible (1 collisions / year) sedimentation accounts for ~ 1. collisions / year

29 And if the answer is YES, is the contaminant co-transport realistic? Conditions: avg. particle size 2 µm avg. pore size 1 µm porosity 3% GW renewal 3 mm/h attachment efficiency = Kd of contaminant = 1 - radius 1-8 m (1 nm) 1-7 m (1 nm) 1 m diffusion coefficient 2.1 x 1-11 m² s x 1-12 m² s -1 Brownian displacement 39 µm h µm h -1 settling rate (D2.6).8 µm h -1 8 µm h -1 steady state, saturated, non-transient conditions concentration ENP in soil: ~ 1 mg/l concentration of matrix: 1.82 g/l ratio of ENP to matrix:.6*1-6 equilibration of contaminant in source: ~ : transported for 1 year through clean soil groundwater

30 radius diffusion coefficient Brownian displacement settling rate (D2.6) 1-8 m (1 nm) 2.1 x 1-11 m² s µm h -1.8 µm h m (1 nm) 2.1 x 1-12 m² s µm h -1 8 µm h -1 1 m what are the critical parameters? groundwater preferential transport of particles (not much information) very large Kd values for the contaminant/enp (unlikely) very low desorption kinetic (not much information)

31 conclusions & outlook natural nanoparticles are complex and heterogeneous systems they are still poorly understood abs. and fluo. signal in arbitrary unit Fe 7 absorption = 26 nm fluorescence = 3/4 nm 6 6 Fe fluorescence Fe molecular weight (amu) Fe in µg L -1 in natural complexity they are seldom described quantitatively NPs are mobile, but mobility and appearance of free NP seems limited contaminants as Pb seem to be predominantly bound to Fe / Mn / Ti phases DOM sites (neq L -1 ) NOM sites ; Fe (neq L -1 ) 1 DOM org 1 Fe original Al original Ca original retention volume V ret (ml) DOM org DOM org 1 DOM sc. to Fe Fe-DOM (Fe part) 1 Fe Pb org V ret (ml) V ret (ml) NOM sites; Fe-part (neq L-1) Fe, Al, Ca (neq L -1 ).1.. Pb (neq L-1) presence of well defined & stable mineral phases ~ 1 nm trace elements distribute specifically between different NP phases (& sizes) aggregates and agglomerates: more clarification or confusion? co-transport of contaminants with ENP is limited but possible important to look at the important controlling processes! are those ENPs (which we look at currently) really so different from natural ones?

32 Thank you! With support from: Elisabeth Neubauer, Samuel Legros, Martin Hassellov, Philippe Le Coustumer, Lei Shi.

conclusions & outlook Trace elements are associated with smaller non-clay type NPs and the NOM Pb seems to be predominantly bound to Fe / (Mn) / Ti phases abs. and fluo.

(& sizes) Redox processes lead to continuing re-formation and re-distribution 1 2 1 3 1 4 1 1 6 molecular weight (amu) DOM sites (neq L -1 ) NOM sites ; Fe (neq L -1 ) 1 DOM org 1 Fe original Al

33 conclusions & outlook Trace elements are associated with smaller non-clay type NPs and the NOM Pb seems to be predominantly bound to Fe / (Mn) / Ti phases abs. and fluo. signal in arbitrary unit Fe 7 absorption = 26 nm fluorescence = 3/4 nm 6 6 Fe fluorescence Fe Fe in µg L -1 trace elements distribute specifically between different NP phases (& sizes) Redox processes lead to continuing re-formation and re-distribution molecular weight (amu) DOM sites (neq L -1 ) NOM sites ; Fe (neq L -1 ) 1 DOM org 1 Fe original Al original Ca original retention volume V ret (ml) DOM org DOM org 1 DOM sc. to Fe Fe-DOM (Fe part) 1 Fe Pb org V ret (ml) V ret (ml) NOM sites; Fe-part (neq L-1) Fe, Al, Ca (neq L -1 ).1.. Pb (neq L-1) size-separation alone is not sufficient to explain the processes chemical speciation at the nanoscale is required (spatial resolution, sensitivity)

NANOPARTICLE SEPARATION: AQUEOUS EXTRACTION

34 NANOPARTICLE SEPARATION: AQUEOUS EXTRACTION METHODOLOGY 1. 4 g sediment + 4 ml.1 M NaCl 2. centrifuged at 4rpm, 9 min 3. supernatant drained, sediment washed multiple times with MQ water 4. when supernatant returns turbid: 2nm cutoff collect supernant von derkammer2

35 LIGHT SCATTERING SAMPLE 2 MEAN SIZE = 271 nm 1μ 2 nm quartz albite mica montmorillonite orthoclase illite nontronite mircocline paragonite pyrophillite muscovite

36 Field Flow Fractionation pump PC control FFF channel detector elution profiles particle size distributions field force diffusion height ~.2 mm accumulation wall FFF channel (side view)

37 Flow-Field Flow Fractionation analytical separation of NPs according to diffusion coefficient HPLC-pump ICP-MS TEM / SEM FFF channel dynamic light scattering UV-DAD fluorescence 18 angle static light scattering MALLS size concentration & 3D spectra M W and R g diff. coefficient -> R h 37

38 Investigating the labile and strongly bound fractions by Chelex extraction Original sample: shaking 6 days as is Chelex sample: shaking 6 days with 2 g Chelex /2mL of sample absorbtion 27 nm & fluorescence 3/ nm in a.u chelex 12 original UV-VIS 4 2 flourescence original NOM UV max = 3, g mol -1 FL max = 1,7 g mol -1 chelex NOM UV max = 2,2 g mol -1 FL max = 1,6 g mol -1 molecular weight in g mol -1

39 Irradiation experiments 24h: decrease of low Mw humic/fulvic acids

40 Irradiation experiments: decrease of low Mw humic/fulvic acids and buildup of aggregates

41 Irradiation experiments: loss of Fe & Pb from low Mw weight to aggregates

42 Milltown Sediment Release As Milltown Sediment Release Arsenic Concentrations Cu Milltown Sediment Release Copper Concentrations As (ppm) 2 1 Milltown Dam Cu (ppm) 1 1 Milltown Dam Kilometers from Milltown Dam Kilometers from Milltown Dam upstream downstream Clark Fork riverbed mud: post dam breaching tributaries (used for background levels at time of sampling) USGS data from 24, 2 and 26 (pre dam breaching) J.M. Moore 28

43 Milltown Dam Removal 1,6 t As 1,6 t Pb 13, t Cu 2, t Zn Moore and Luoma 199

Detection of engineered cerium oxide nanoparticles in soils

Detection of engineered cerium oxide nanoparticles in soils Frank von der Kammer Antonia Praetorius Willi Fabienke Thilo Hofmann Department of Environmental Geosciences University of Vienna Austria identification