Transformation and release of micronized Cu used as a wood preservative in treated wood in wetland soil

Highlights: • Micronized Malachite replaces chromated copper arsenate as a wood preservative. • The concern is that nano-sized Malachite may escape from treated-wood. • Malachite treated wood in wetland mesocosms released Cu²⁺ to soil and water. • Wetland soil Cu speciation showed Cu(II and I) organics, Cu on Fe oxides, and Cu₂S. • No evidence of nano-sized Malachite [Cu₂CO₃(OH)2] escapement was found. Micronized Cu (μ-Cu) is used as a wood preservative, replacing toxic chromated copper arsenate (CCA). Micronized Cu is malachite [Cu₂CO₃(OH)₂] that has been milled to micron/submicron particles, with many particle diameters less than 100 nm, mixed with biocides and then used to treat wood. In addition to concerns about the fate of the Cu from μ-Cu, there is interest in the fate of the nano-Cu (n-Cu) constituents. We examined movement of Cu from μ-Cu-treated wood after placing treated-wood stakes into model wetland ecosystems. Release of Cu into surface and subsurface water was monitored. Surface water Cu reached maximum levels 3 days after stake installation and remained elevated if the systems remained inundated. Subsurface water Cu levels were 10% of surface water levels at day 3 and increased gradually thereafter. Sequential filtering indicated that a large portion of the Cu in solution was associating with soluble organics, but there was no evidence for n-Cu in solution. After 4 months, Cu in thin-sections of treated wood and adjacent soil were characterized with micro X-ray absorption fine structure spectroscopy (μ-XAFS). Localization and speciation of Cu in the wood and adjacent soil using μ-XAFS clearly indicated that Cu concentrations decreased over time in the treated wood and increased in the adjacent soil. However, n-Cu from the treated wood was not found in the adjacent soil or plant roots. The results of this study indicate that Cu in the μ-Cu-treated wood dissolves and migrates into adjacent soil and waters primarily in ionic form (i.e., Cu²⁺) and not as nano-sized Cu particles. A reduced form of Cu (Cu₂S) was identified in deep soil proximal to the treated wood, indicating strong reducing conditions. The formation of the insoluble Cu₂S effectively removes some portion of dissolved Cu from solution, reducing movement of Cu²⁺ to the water column and diminishing exposure.