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Title: Pb, Cu, and Zn distributions at humic acid-coated metal-oxide surfaces

Journal Article · · Geochimica et Cosmochimica Acta
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [8];  [9]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Univ. of Chicago, Chicago, IL (United States)
  5. Stanford Univ., Stanford, CA (United States); CEREGE, Europole Mediterraneen de l'Arbois, Cedex (France)
  6. Stanford Univ., Stanford, CA (United States); Ben-Gurion Univ. of the Negev, Midreshet Ben-Gurion (Israel)
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  9. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
+ Show Author Affiliations

Mineral surfaces are often coated by natural organic matter (NOM), which has a major influence on metal-ion sorption and sequestration because of the abundance of binding sites in such coatings and the changes they cause in local nanoscale environments. The effects of NOM coatings on mineral surfaces are, however, still poorly understood at the molecular level due to the complexity of these systems. We have applied long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy to measure the partitioning of naturally present Cu(II) (0.0226%), Zn(II) (0.009%), and Pb(II) (similar to 0.0004%) between Elliott Soil Humic Acid (ESHA) coatings and three model single-crystal metal-oxide substrates: alpha-Al2O3 (00 01), alpha-Al2O3 (1-102), and alpha-Fe2O3 (0001). The competitive sorption effects among these metal ions for binding sites in the ESHA coatings and on the metal-oxide surfaces were investigated as a function of reaction time, calcium content, and solution pH. Pb(II) ions present in the ESHA coatings were found to redistribute to reactive alpha-Al2O3 (1-102) and alpha-Fe2O3 (0001) surfaces after 3 h of reaction (pH = 6.0, [Ca(II)] = 2 mM). Pb(II) partitioning onto these reactive metal-oxide surfaces increased with increasing reaction time (up to 7 d). Additionally, the partitioning of Cu(II) and Zn(II) from the ESHA coating to the alpha-Fe2O3 (0001) substrate increased slightly with reaction time (2.4% and 3.7% for Cu(II) and Zn(II), respectively, after 3 h and 6.4% and 7.7% for Cu(II) and Zn(II), respectively, after 72 h of reaction time). However, no changes in the partitioning of Cu(II) and Zn(II) onto the alpha-Al2O3 (1-102) surface were observed with increasing reaction time, suggesting that these ions strongly complex with functional groups in the ESHA coatings. Similar results were obtained for Cu(II) and Zn(II) on the ESHA-coated alpha-Al2O3 (1-102) surfaces in samples without the addition of calcium. However, the amounts of Pb(II) mobilized from the ESHA coatings onto the alpha-Al2O3 (1-102) surfaces increased from 40% (no added Ca) to 58% (with 2 mM Ca) after 72 h of reaction time, possibly due to displacement of Pb(II) by Ca(II) from binding sites in the ESHA coatings. In contrast, Pb(II), Cu(II), and Zn(II) present in the ESHA coatings were found to be unreactive with the alpha-Al2O3 (0001) surface. The reactivities of the three ESHA-coated metal-oxide surfaces that we observed, with respect to metal-ion sorption, are consistent with the trend observed for the uncoated metal-oxide surfaces: alpha-Fe2O3 (0001) > alpha-Al2O3 (1-102) > alpha-Al2O3 (0001). In addition, Pb(II) partitioning onto alpha-Al2O3 (1-102) surfaces increased with increasing pH from 4.0 to 9.0 as a result of the increasingly negative surface charge. Our results show that intrinsic properties (nature of binding sites, binding affinities, and surface charge) of the ESHA coatings and metal-oxide surfaces, as well as external parameters such as pH and competing ions, are key factors governing the distribution and speciation of metal ions at complex NOM/mineral interfaces.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357; FG02-94ER14466; AC02-05CH11231
OSTI ID:
1327773
Alternate ID(s):
OSTI ID: 1340232; OSTI ID: 1430546
Journal Information:
Geochimica et Cosmochimica Acta, Vol. 188, Issue C; ISSN 0016-7037
Publisher:
The Geochemical Society; The Meteoritical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

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Cited By (4)

Immobilization of heavy metals in contaminated soil after mining activity by using biochar and other industrial by-products: the significant role of minerals on the biochar surfaces journal May 2018
Fulvic acid in foliar spray is more effective than humic acid via soil in improving coffee seedlings growth text January 2019
Fulvic acid in foliar spray is more effective than humic acid via soil in improving coffee seedlings growth journal March 2019
Fulvic acid in foliar spray is more effective than humic acid via soil in improving coffee seedlings growth text January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
humic acid
Pb
Cu
Zn
Ca
metal-oxide surfaces
single crystal
X-ray standing wave
LP-XSW-FY
metal partitioning
hematite
alumina
pH effect
36 MATERIALS SCIENCE
58 GEOSCIENCES
X-RAYS
COMPETITIVE ADSORPTION
ION-BINDING
MINERAL SURFACES
NATURAL ORGANIC-MATTER
RAY STANDING WAVES