Mark Durenkamp

Fate of Zinc Oxide and Silver Nanoparticles in a Pilot Wastewater Treatment Plant and in Processed Biosolids

Chemical transformations of silver nanoparticles (Ag NPs) and zinc oxide nanoparticles (ZnO NPs) during wastewater treatment and sludge treatment must be characterized to accurately assess the risks that these nanomaterials pose from land application of biosolids. Here, X-ray absorption spectroscopy (XAS) and supporting characterization methods are used to determine the chemical speciation of Ag and Zn in sludge from a pilot wastewater treatment plant (WWTP) that had received PVP coated 50 nm Ag NPs and 30 nm ZnO NPs, dissolved metal ions, or no added metal. The effects of composting and lime and heat treatment on metal speciation in the resulting biosolids were also examined. All added Ag was converted to Ag2S, regardless of the form of Ag added (NP vs ionic). Zn was transformed to three Zn-containing species, ZnS, Zn3(PO4)2, and Zn associated Fe oxy/hydroxides, also regardless of the form of Zn added. Zn speciation was the same in the unamended control sludge. Ag2S persisted in all sludge treatments. Zn3(PO4)2 persisted in sludge and biosolids, but the ratio of ZnS and Zn associated with Fe oxy/hydroxide depended on the redox state and water content of the biosolids. Limited differences in Zn and Ag speciation among NP-dosed, ion-dosed, and control biosolids indicate that these nanoparticles are transformed to similar chemical forms as bulk metals already entering the WWTP.

Nanomaterials in Biosolids Inhibit Nodulation, Shift Microbial Community Composition, and Result in Increased Metal Uptake Relative to Bulk/Dissolved Metals.

We examined the effects of amending soil with biosolids produced from a pilot-scale wastewater treatment plant containing a mixture of metal-based engineered nanomaterials (ENMs) on the growth of Medicago truncatula, its symbiosis with Sinorhizobium meliloti, and on soil microbial community structure. Treatments consisted of soils amended with biosolids generated with (1) Ag, ZnO, and TiO2 ENMs introduced into the influent wastewater (ENM biosolids), (2) AgNO3, Zn(SO4)2, and micron-sized TiO2 (dissolved/bulk metal biosolids) introduced into the influent wastewater stream, or (3) no metal added to influent wastewater (control). Soils were amended with biosolids to simulate 20 years of metal loading, which resulted in nominal metal concentrations of 1450, 100, and 2400 mg kg(-1) of Zn, Ag, and Ti, respectively, in the dissolved/bulk and ENM treatments. Tissue Zn concentrations were significantly higher in the plants grown in the ENM treatment (182 mg kg(-1)) compared to those from the bulk treatment (103 mg kg(-1)). Large reductions in nodulation frequency, plant growth, and significant shifts in soil microbial community composition were found for the ENM treatment compared to the bulk/dissolved metal treatment. These results suggest differences in metal bioavailability and toxicity between ENMs and bulk/dissolved metals at concentrations relevant to regulatory limits.

Nanoparticles within WWTP sludges have minimal impact on leachate quality and soil microbial community structure and function.

One of the main pathways by which engineered nanoparticles (ENPs) enter the environment is through land application of waste water treatment plant (WWTP) sewage sludges. WWTP sludges, enriched with Ag and ZnO ENPs or their corresponding soluble metal salts during anaerobic digestion and subsequently mixed with soil (targeting a final concentration of 1400 and 140 mg/kg for Zn and Ag, respectively), were subjected to 6 months of ageing and leaching in lysimeter columns outdoors. Amounts of Zn and Ag leached were very low, accounting for <0.3% and <1.4% of the total Zn and Ag, respectively. No differences in total leaching rates were observed between treatments of Zn or Ag originally input to WWTP as ENP or salt forms. Phospholipid fatty acid profiling indicated a reduction in the fungal component of the soil microbial community upon metal exposure. However, overall, the leachate composition and response of the soil microbial community following addition of sewage sludge enriched either with ENPs or metal salts was very similar.

Monte Carlo simulations of the transformation and removal of Ag, TiO2, and ZnO nanoparticles in wastewater treatment and land application of biosolids

The use of nano-enabled materials in industry and consumer products is increasing rapidly and with it, the more imperative it becomes to understand the consequences of such materials entering the environment during production, use or disposal. The novel properties of engineered nanomaterials (ENMs) that make them desirable for commercial applications also present the possibility of impacting aquatic and terrestrial environments in ways that may differ from materials in bulk format. Modeling techniques are needed to proactively predict the environmental fate and transport of nanomaterials. A model for nanoparticle (NP) separation and transformation in water treatment was parameterized for three metal and metal-oxide NPs. Functional assays to determine NP specific distribution and transformation were used to parameterize the model and obtain environmentally relevant concentrations of NPs and transformation byproducts leaving WWTPs in effluent and biosolids. All three NPs were predicted to associate >90% with the solid phase indicating significant accumulation in the biosolids. High rates of transformation for ZnO and Ag NPs resulted in ~97% transformation of the NPs that enter the plant despite differences in transformation rate in aerobic versus anaerobic environments. Due to high insolubility and negligible redox transformation, the only process predicted to impact TiO2 NP fate and transport in WWTPs was distribution between the solid and liquid phases. Subsequent investigation of ZnO NP species fate and transport when land applied in biosolids indicated that steady state concentrations of ZnO phases would likely be achieved after approximately 150days under loading conditions of biosolids typical in current practice.

Sewage sludge treated with metal nanomaterials inhibits earthworm reproduction more strongly than sludge treated with metal metals in bulk/salt forms

Earthworms were exposed to soils amended with sewage sludges from a wastewater treatment plant (WWTP) treated with nanomaterials (ENMs) or metal/ionic salts. Sewage sludges were generated with either no metal added to the WWTP influent (control), ionic ZnO, AgNO3 and bulk (micron sized) TiO2 added (ionic metal-treated) or ZnO, Ag and TiO2 ENMs added (ENM-treated). A sandy-loam soil was amended with the treated sewage sludge and aged in outdoor lysimeters for six months. Earthworms were exposed to the aged mixtures and a dilution of the mixtures (using control soil–sludge mix). Separate earthworm exposures to as-synthesized ENM and ionic metals salts (Zn/Ag singly) were carried out in the same soil. Earthworm reproduction was depressed by 90% in the high-metal ENM treatment and by 22–27% in the ionic metal and low-metal ENM soil–sludge treatments. Based on total metal concentrations in the soil–sludges the as-synthesised metal salt and ENM exposures predicted Zn was driving observed toxicity in the soil–sludge more than Ag. Earthworms from the high-metal ENM treatment accumulated significantly more Ag than other treatments whereas total Zn concentrations in the earthworms were within the range for earthworm Zn regulation for all treatments. This study suggests that current Zn limits set to provide protection against ionic metal forms may not protect soil biota where metals are input to WWTP in the ENM form.