Copper and Gold Nanoparticles Increase Nutrient Excretion Rates of Primary Consumers.

Freshwater ecosystems are exposed to engineered nanoparticles through municipal and industrial wastewater-effluent discharges and agricultural nonpoint source runoff. Because previous work has shown that engineered nanoparticles from these sources can accumulate in freshwater algal assemblages, we hypothesized that nanoparticles may affect the biology of primary consumers by altering the processing of two critical nutrients associated with growth and survivorship, nitrogen and phosphorus. We tested this hypothesis by measuring the excretion rates of nitrogen and phosphorus of Physella acuta, a ubiquitous pulmonate snail that grazes heavily on periphyton, exposed to either copper or gold engineered nanoparticles for 6 months in an outdoor wetland mesocosm experiment. Chronic nanoparticle exposure doubled nutrient excretion when compared to the control. Gold nanoparticles increased nitrogen and phosphorus excretion rates more than copper nanoparticles, but overall, both nanoparticles led to higher consumer excretion, despite contrasting particle stability and physiochemical properties. Snails in mesocosms enriched with nitrogen and phosphorus had overall higher excretion rates than ones in ambient (no nutrients added) mesocosms. Stimulation patterns were different between nitrogen and phosphorus excretion, which could have implications for the resulting nutrient ratio in the water column. These results suggest that low concentrations of engineered nanoparticles could alter the metabolism of consumers and increase consumer-mediated nutrient recycling rates, potentially intensifying eutrophication in aquatic systems, for example, the increased persistence of algal blooms as observed in our mesocosm experiment.

Guiding the design space for nanotechnology to advance sustainable crop production.

The globally recognized need to advance more sustainable agriculture and food systems has motivated the emergence of transdisciplinary solutions, which include methodologies that utilize the properties of materials at the nanoscale to address extensive and inefficient resource use. Despite the promising prospects of these nanoscale materials, the potential for large-scale applications directly to the environment and to crops necessitates precautionary measures to avoid unintended consequences. Further, the effects of using engineered nanomaterials (ENMs) in agricultural practices cascade throughout their life cycle and include effects from upstream-embodied resources and emissions from ENM production as well as their potential downstream environmental implications. Building on decades-long research in ENM synthesis, biological and environmental interactions, fate, transport and transformation, there is the opportunity to inform the sustainable design of nano-enabled agrochemicals. Here we perform a screening-level analysis that considers the system-wide benefits and costs for opportunities in which ENMs can advance the sustainability of crop-based agriculture. These include their on-farm use as (1) soil amendments to offset nitrogen fertilizer inputs, (2) seed coatings to increase germination rates and (3) foliar sprays to enhance yields. In each analysis, the nano-enabled alternatives are compared against the current practice on the basis of performance and embodied energy. In addition to identifying the ENM compositions and application approaches with the greatest potential to sustainably advance crop production, we present a holistic, prospective, systems-based approach that promotes emerging alternatives that have net performance and environmental benefits.

Speciation of Mercury in Selected Areas of the Petroleum Value Chain.

Petroleum, natural gas, and natural gas condensate can contain low levels of mercury (Hg). The speciation of Hg can affect its behavior during processing, transport, and storage so efficient and safe management of Hg requires an understanding of its chemical form in oil, gas and byproducts. Here, X-ray absorption spectroscopy was used to determine the Hg speciation in samples of solid residues collected throughout the petroleum value chain including stabilized crude oil residues, sediments from separation tanks and condensate glycol dehydrators, distillation column pipe scale, and biosludge from wastewater treatment. In all samples except glycol dehydrators, metacinnabar (ß-HgS) was the primary form of Hg. Electron microscopy on particles from a crude sediment showed nanosized (<100 nm) particles forming larger aggregates, and confirmed the colocalization of Hg and sulfur. In sediments from glycol dehydrators, organic Hg(SR)2 accounted for ∼60% of the Hg, with ∼20% present as ß-HgS and/or Hg(SR)4 species. ß-HgS was the predominant Hg species in refinery biosludge and pipe scale samples. However, the balance of Hg species present in these samples depended on the nature of the crude oil being processed, i.e. sweet (low sulfur crudes) vs sour (higher sulfur crudes). This information on Hg speciation in the petroleum value chain will inform development of better engineering controls and management practices for Hg.

Time and Nanoparticle Concentration Affect the Extractability of Cu from CuO NP-Amended Soil.

We assess the effect of CuO nanoparticle (NP) concentration and soil aging time on the extractability of Cu from a standard sandy soil (Lufa 2.1). The soil was dosed with CuO NPs or Cu(NO3)2 at 10 mg/kg or 100 mg/kg of total added Cu, and then extracted using either 0.01 M CaCl2 or 0.005 M diethylenetriaminepentaacetic acid (DTPA) (pH 7.6) extraction fluid at selected times over 31 days. For the high dose of CuO NPs, the amount of DTPA-extractable Cu in soil increased from 3 wt % immediately after mixing to 38 wt % after 31 days. In contrast, the extractability of Cu(NO3)2 was highest initially, decreasing with time. The increase in extractability was attributed to dissolution of CuO NPs in the soil. This was confirmed with synchrotron X-ray absorption near edge structure measurements. The CuO NP dissolution kinetics were modeled by a first-order dissolution model. Our findings indicate that dissolution, concentration, and aging time are important factors that influence Cu extractability in CuO NP-amended soil and suggest that a time-dependent series of extractions could be developed as a functional assay to determine the dissolution rate constant.

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.

Field-scale transport and transformation of carboxymethylcellulose-stabilized nano zero-valent iron.

The fate of nano zerovalent iron (nZVI) during subsurface injection was examined using carboxymethylcellulose (CMC) stabilized nZVI in a very large three-dimensional physical model aquifer with detailed monitoring using multiple, complementary detection methods. A fluorescein tracer test in the aquifer plus laboratory column data suggested that the very-aggressive flow conditions necessary to achieve 2.5 m of nZVI transport could be obtained using a hydraulically constrained flow path between injection and extraction wells. However, total unoxidized nZVI was transported only about 1 m and <2% of the injected nZVI concentration reached that distance. The experimental data also indicated that groundwater flow changed during injection, likely due to hydrogen bubble formation, which diverted the nZVI away from the targeted flow path. The leading edge of the iron plume became fully oxidized during transport. However, within the plume, oxidation of nZVI decreased in a fashion consistent with progressive depletion of aquifer "reductant demand". To directly quantify the extent of nZVI transport, a spectrophotometric method was developed, and the results indicated that deployment of unoxidized nZVI for groundwater remediation will likely be difficult.

Partitioning behavior of organic contaminants in carbon storage environments: a critical review.

Carbon capture and storage is a promising strategy for mitigating the CO(2) contribution to global climate change. The large scale implementation of the technology mandates better understanding of the risks associated with CO(2) injection into geologic formations and the subsequent interactions with groundwater resources. The injected supercritical CO(2) (sc-CO(2)) is a nonpolar solvent that can potentially mobilize organic compounds that exist at residual saturation in the formation. Here, we review the partitioning behavior of selected organic compounds typically found in depleted oil reservoirs in the residual oil-brine-sc-CO(2) system under carbon storage conditions. The solubility of pure phase organic compounds in sc-CO(2) and partitioning of organic compounds between water and sc-CO(2) follow trends predicted based on thermodynamics. Compounds with high volatility and low aqueous solubility have the highest potential to partition to sc-CO(2). The partitioning of low volatility compounds to sc-CO(2) can be enhanced by cosolvency due to the presence of higher volatility compounds in the sc-CO(2). The effect of temperature, pressure, salinity, pH, and dissolution of water molecules into sc-CO(2) on the partitioning behavior of organic compounds in the residual oil-brine-sc-CO(2) system is discussed. Data gaps and research needs for models to predict the partitioning of organic compounds in brines and from complex mixtures of oils are presented. Models need to be able to better incorporate the effect of salinity and cosolvency, which will require more experimental data from key classes of organic compounds.

Meditations on the ubiquity and mutability of nano-sized materials in the environment.

A wide variety of nanomaterials can be found naturally occurring in the environment, although finding and characterizing these materials remains a challenge due to their size. Recent studies in the field have shown that natural nanomaterials are common in many geochemical systems. In this issue of ACS Nano, Hutchison and co-workers make us realize that manmade nanomaterials can often be practically identical to those that spontaneously form in the environment. This Perspective discusses the prevalence of nanomaterials in nature, including anthropogenic and naturally occurring nanomaterials, and the dynamic behavior of these materials in the environment.