Exposure of humic acid-coated goethite colloids to groundwater does not affect their adsorption of metal(loid)s and their impact on Daphnid mobility

Marie Mollenkopf, Andreas Fritzsche, Daniela Montalvo, Maria Diez-Ortiz, Verónica González-Andrés, Erik Smolders, Rainer Meckenstock, Kai Uwe Totsche

Research output: Contribution to journalArticlepeer-review

4 Scopus citations


Engineered humic acid-coated goethite (HA-Goe) colloids find increasing application in in situ remediation of metal(loid)-polluted groundwater. Once introduced into the subsurface, the colloids interact with groundwater altering their physicochemical properties. In comparison to freshly synthesized, unreacted HA-Goe colloids, such alterations could reduce the adsorption affinity towards metal(loid)s and also result in altered ecotoxicological effects. In our study, HA-Goe colloids were exposed to two groundwaters (low vs. high concentrations of metal(loid)s) from two metal(loid)-contaminated sites for 87 days. We investigated (i) the course of HA-Goe ecotoxicity (Daphnia magna immobilization tests), (ii) HA-Goe adsorption properties (multi-element solutions containing As, Cu, Zn, Ni and Co), and (iii) changes in the chemical composition as well as in the mineral and aggregate properties of HA-Goe. The adsorption affinity of HA-Goe decreased in the order As ≈ Cu ≫ Zn > Ni ≈ Co. The metal(loid) adsorption occurred rapidly after mixing prior to the first sampling, while the duration of ongoing exposition to groundwater had no effect on the adsorption of these metal(loid)s. We neither observed a desorption of humic acids from the goethite surface nor alterations in the mineralogy, crystallinity, and surface properties of HA-Goe. Standardized Daphnia magna immobilization tests showed an increased number of mobile organisms with increasing exposure time of HA-Goe to both groundwaters. The decrease in HA-Goe-mediated immobilization of D. magna was strongest within the first 30 d. We attribute this to a shift to smaller sizes due to the breakdown of large HA-Goe aggregates, particularly within the first 30 d. The breakdown of these μm-sized aggregates may result mainly from the repeated shaking of the HA-Goe suspensions. Our study confirms within this particular setting that the tested HA-Goe colloids are suitable for the long-term immobilization of metal(loid)s, while lethal effects on D. magna were negligible.

Original languageEnglish
Article number149153
JournalScience of the Total Environment
StatePublished - 25 Nov 2021
Externally publishedYes


  • Aging
  • Daphnia magna
  • Heavy metals
  • Iron oxide colloids
  • Nanoparticles
  • Remediation


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