Linking the Environmental Pressures of China's Capital Development to Global Final Consumption of the Past Decades and into the Future.

China's rapid growth was fueled by investments that grew more than 10-fold since 1995. Little is known about how the capital assets acquired, while being used in productive processes for years or decades, satisfy global final consumption of goods and services, or how the resource use and emissions that occurred during capital formation are attributable to past or future consumption. Here, enabled by a new global model of capital formation and use, we quantify the linkages over the past 2 decades and into the future between six environmental pressures (EPs) associated with China's capital formation and attributable to Chinese as well as non-Chinese consumption. We show that only 35% of the capital assets acquired by China from 1995 to 2015, representing 32-39% of the associated EPs (e.g., water consumption, greenhouse gas (GHG) emissions, and metal ore extractions), have been depreciated, while the majority rest will serve future production and consumption. The outsourcing of capital services and the associated EPs are considerable, ranging from 14 to 25% of depending on the EP indicators. Without accounting for the capital-final consumption linkages across time and space, one would miscalculate China's environmental footprints related to the six EPs by big margins, from -61% to +114%.

Nano-structural effects on Hematite (α-Fe2O3) nanoparticle radiofrequency heating.

Nano-sized hematite (α-Fe2O3) is not well suited for magnetic heating via an alternating magnetic field (AMF) because it is not superparamagnetic-at its best, it is weakly ferromagnetic. However, manipulating the magnetic properties of nano-sized hematite (i.e., magnetic saturation (Ms), magnetic remanence (Mr), and coercivity (Hc)) can make them useful for nanomedicine (i.e., magnetic hyperthermia) and nanoelectronics (i.e., data storage). Herein we study the effects of size, shape, and crystallinity on hematite nanoparticles to experimentally determine the most crucial variable leading to enhancing the radio frequency (RF) heating properties. We present the synthesis, characterization, and magnetic behavior to determine the structure-property relationship between hematite nano-magnetism and RF heating. Increasing particle shape anisotropy had the largest effect on the specific adsorption rate (SAR) producing SAR values more than 6 × greater than the nanospheres (i.e., 45.6 ± 3 W/g of α-Fe2O3 nanorods vs. 6.89 W/g of α-Fe2O3 nanospheres), indicating α-Fe2O3 nanorods can be useful for magnetic hyperthermia.

Strategic design and finance of rainwater harvesting to cost-effectively meet large-scale urban water infrastructure needs.

Many cities are confronted with both water scarcity and urban flooding as centralized water infrastructures becoming increasingly inadequate in a changing climate. Decentralized infrastructures like rainwater harvesting (RWH) can ease both issues. Yet, most studies find RWH offers limited infrastructure capacity at high cost. Previous assessments, however, fail to consider two critical advantages: multi-functionality and high adaptability. By improving the incorporation of these advantages in our analysis of 1.06 million buildings with distinct design and water demand characteristics and 20-year hourly precipitation records in New York City (NYC), we demonstrate, contrary to existing studies, that strategically designed, financed and implemented rooftop RWH systems in all or a subset of the buildings can meet large-scale infrastructure development needs for water supply and stormwater management. RWH implementation featuring public-private partnerships (PPP) in 43-96% of the buildings can serve 17-29% of the city's non-drinking water demands while reducing the public expenditure per unit of water supply by 13-85%. The distributed citywide RWH implementations prevent 35-56% of rooftop runoff from entering the sewage system, rivers, and/or waterways per month, with observed rooftop runoff reductions as high as 90% for a single rain event.

Superparamagnetic MOF@GO Ni and Co based hybrid nanocomposites as efficient water pollutant adsorbents.

A series of highly efficient adsorbents were developed using Ni3(BTC)2 and Co3(BTC)2 metal-organic frameworks (MOFs) and Fe3O4 magnetic nanoparticles (MNPs) to functionalize graphene oxide (GO). XRD results show high crystallinity of the prepared nanomaterials and the successful decoration of Ni3(BTC)2 and Co3(BTC)2 MOFs over the GO substrate (BTC = benzene-1,3,5-tricarboxylic acid). SEM and TEM imaging show the successful formation of nanoscale MOFs and Fe3O4 MNPs over GO. IR spectroscopy supports the characterization and successful preparation of the Fe3O4/MOF@GO hybrid composite nanoadsorbents. The prepared composite nanoadsorbents were used to sorb Methylene Blue (MB) as a model for common organic pollutants in water and common ions (Na+, Ca2+, Mg2+, SO42-, SiO32-) from a brackish water model. The adsorbed concentration at equilibrium of MB of the prepared composite nanoadsorbents increases by an average of 30.52 and 13.75 mg/g for the Co and Ni composite, respectively, when compared to the MOFs parent materials. The adsorbed amount of sulfate ions increases by 92.1 mg/g for the Co composite and 112.1 mg/g for the Ni composite, when compared to graphene oxide. This adsorption enhancement is attributed to suppressed aggregation through increased dispersive forces in the MOFs due to the presence of GO, formation of nanoscale MOFs over the GO platform, and the hindering of stacking of the graphene layers by the MOFs. Leaching tests show that the release of Co and Ni ions to water is reduced from 105.2 and 220 mg/L, respectively, in the parent MOF materials to 0.5 and 16.4 mg/L, respectively, in the composite nanoadsorbents. These findings show that the newly developed composite nanoadsorbents can sorb organic pollutants, and target sulfate and silicate anions, which makes them suitable candidates for water and wastewater treatments.

Toward Realizing Multifunctionality: Photoactive and Selective Adsorbents for the Removal of Inorganics in Water Treatment.

Persistent and potentially toxic inorganic oxoanions (e.g., arsenic and selenium) are one class of contaminants of concern in drinking water for which treatment technologies must be improved. Effective removal of these oxoanions is made difficult by the varying adsorption affinity of the different oxidation states, as well as the presence of background ions with similar chemical structure and behavior that strongly compete for adsorption sites, greatly reducing removal efficiencies. Recent studies pointing to the negative health effects of inorganic oxoanion contaminants have resulted or are expected to result in new regulations lowering their allowable maximum concentration level (MCL) in drinking water. While these regulations are intended to protect human and environmental health, they must also allow for balanced economic costs. As such, the MCLs are often set at levels that are not as health protective due to high treatment costs that continue to present a significant challenge for small (500-3300 people) to very small (25-500 people) communities. In this Account, we focus on the development of novel cost-effective, sustainable, and efficient multifunctional and selective adsorbents that offer solutions to the above challenges through two platforms: nanoenabled and transition-metal cross-linked chitosan (TMCC) and crystal facet engineered nanometal oxides (NMO). These complementary platforms offer treatment solutions at different scales and flow rates (e.g., in a point-of-use device versus a small-scale community system). Multifunctional adsorbents combine processes that traditionally require multiple steps offering the potential for reducing treatment time and costs. Development of selective adsorbents can greatly increase removal efficiencies of target contaminants by either promoting their adsorption or hindering adsorption of competitive ions. The following sections describe (1) synthesis of novel nanoenabled waste sourced bioadsorbents; (2) development of multifunctional adsorbents to simultaneously photo-oxidize arsenite and adsorb arsenate; (3) development of a selective adsorbent for removal of arsenate and selenite over phosphate; (4) investigations of the conventional wisdom that increased surface area yields increased oxoanion removal using selenium sorption on nanohematite as a case study; and (5) crystal engineering of nanohematite to promote selenite adsorption. The novel technologies developed through these research efforts can serve as templates for the creation of future adsorbents tailored for use targeting other oxoanion contaminants of interest.

Preferential adsorption of selenium oxyanions onto {1 1 0} and {0 1 2} nano-hematite facets.

As the commercial use of nano metal oxides, including iron oxides, becomes more prevalent, there is a need to understand functionality as it relates to the inherent properties of the nanomaterial. Many applications of nanomaterials rely on adsorption, ranging from catalysis to aqueous remediation. In this paper, adsorption of selenium (Se), an aqueous contaminant, is used as a model sorbate to elucidate the relationships of structure, property, and (adsorptive) function of nano-hematite (nα-Fe2O3). As such, six nα-Fe2O3 particles were synthesized controlling for size, shape and surface area without capping agents. Sorbent characteristics of the six particles were then assessed for their impact on selenite (HSeO3-) and selenate (SeO42-) adsorption capacity and mechanism. Mechanism was assessed using in-situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and extended X-ray absorption fine edge spectroscopy (EXAFS). Regression analyses were then performed to determine which characteristics best describe adsorption capacity and binding mechanisms of Se on nα-Fe2O3. The results demonstrate that crystal surface structure, specifically presence of the {0 1 2} facet promotes adsorption of Se and the presence of {0 1 2} facets promotes SeO42- sorption to a greater extent than HSeO3-. The data further indicates that {1 1 0} facets bind HSeO3- with binuclear complexes while {0 1 2} facets bind HSeO3- via mononuclear inner-sphere complexes. Specific nα-Fe2O3 facets also likely direct the ratio of inner to outer-sphere complexes in SeO42- adsorption.

Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO2 to CO conversion via the reverse water-gas shift reaction.

Understanding how nano-dimensionality impacts iron oxide based catalysis is central to a wide range of applications. Here, we focus on hematite nanosheets, nanowires and nanoparticles as applied to catalyze the reverse water gas shift (RWGS) probe reaction. We introduce a novel approach to synthesize ultrathin (4-7 nm) hematite nanosheets using copper oxide nanosheets as a hard template and propose a reaction mechanism based on density functional theory (DFT) calculations. Hematite nanowires and nanoparticles were also synthesized and characterized. H2 temperature programmed reduction (H2-TPR) and RWGS reactions were performed to glean insights into the mechanism of CO2 conversion to CO over the iron oxide nanomaterials and were compared to H2 binding energy calculations based on density functional theory. While the nanosheets did exhibit high CO2 conversion, 28% at 510 °C, we found that the iron oxide nanowires had the highest CO2 conversion, reaching 50% at 750 °C under atmospheric pressure. No products besides CO and H2O were detected.

The role of counter ions in nano-hematite synthesis: Implications for surface area and selenium adsorption capacity.

Nano metal oxides are of interest for aqueous selenium (Se) remediation, and as such, nano-hematite (nα-Fe2O3) was examined for use as a Se adsorbent. The effect of surface area on adsorption was also studied. nα-Fe2O3 particles were synthesized from Fe(NO3)3 and FeCl3 via forced hydrolysis. The resulting particles have similar sizes, morphologies, aggregate size, pore size, and PZC. The nα-Fe2O3 from FeCl3 (nα-Fe2O3-C) differs from the nα-Fe2O3 from Fe(NO3)3 (nα-Fe2O3-N) with a ∼25±2m(2)/g greater surface area. Selenite Se(IV) adsorption capacity on nα-Fe2O3 has a qmax ∼17mg/g for the freeze-dried and re-suspended nα-Fe2O3. The Δqmax for nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension was 4.6mg/g. For selenate Se(VI), the freeze-dried and re-suspended particles realize a Δqmax= 1.5mg/g for nα-Fe2O3 from Fe(NO3)3 and FeCl3. The nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension demonstrated Se(VI) Δqmax=5.4mg/g. In situ ATR-FTIR isotherm measurements completed for Se(VI) at a pH 6 suggest that Se(VI) forms primarily outer-sphere complexes with nα-Fe2O3 synthesized from both salts.

Towards a selective adsorbent for arsenate and selenite in the presence of phosphate: Assessment of adsorption efficiency, mechanism, and binary separation factors of the chitosan-copper complex.

The potential for a chitosan-copper polymer complex to select for the target contaminants in the presence of their respective competitive ions was evaluated by synthesizing chitosan-copper beads (CCB) for the treatment of (arsenate:phosphate), (selenite:phosphate), and (selenate:sulfate). Based on work by Rhazi et al., copper (II) binds to the amine moiety on the chitosan backbone as a monodentate complex (Type I) and as a bidentate complex crosslinking two polymer chains (Type II), depending on pH and copper loading. In general, the Type I complex exists alone; however, beyond threshold conditions of pH 5.5 during synthesis and a copper loading of 0.25 mol Cu(II)/mol chitosan monomer, the Type I and Type II complexes coexist. Subsequent chelation of this chitosan-copper ligand to oxyanions results in enhanced and selective adsorption of the target contaminants in complex matrices with high background ion concentrations. With differing affinities for arsenate, selenite, and phosphate, the Type I complex favors phosphate chelation while the Type II complex favors arsenate chelation due to electrostatic considerations and selenite chelation due to steric effects. No trend was exhibited for the selenate:sulfate system possibly due to the high Ksp of the corresponding copper salts. Binary separation factors, α12, were calculated for the arsenate-phosphate and selenite-phosphate systems, supporting the mechanistic hypothesis. While, further research is needed to develop a synthesis method for the independent formation of the Type II complexes to select for target contaminants in complex matrices, this work can provide initial steps in the development of a selective adsorbent.

Adsorption of selenite and selenate by nanocrystalline aluminum oxide, neat and impregnated in chitosan beads.

Nanocrystalline metal oxide impregnated chitosan beads (MICB) were successfully developed with nanocrystalline aluminum oxide (n-Al2O3) to form n-Al2O3 impregnated chitosan beads (AICB). AICB were able to simultaneously adsorb inorganic aqueous selenite and selenate more effectively than n-Al2O3 or chitosan alone. For completeness, adsorption performance was also compared to n-TiO2, a widely studied adsorbent for selenium, and n-TiO2 impregnated chitosan beads (TICB). For the selenite system, n-Al2O3 was the primary active adsorbent responsible for removal as chitosan has a low affinity for selenite. For selenate, however, chitosan was the primary active adsorbent. The association constants for the adsorbent/adsorbate complexes and the relative amounts in which they are present supported this hypothesis. The association constants for selenate binding on n-Al2O3 and chitosan were 1.215 × 10(-2) and 3.048 × 10(-3), respectively, and the association constants for selenite binding on n-Al2O3 and chitosan were 1.349 × 10(-2) and 1.990 × 10(-4), respectively. For systems with coexisting selenite and selenate, AICB is potentially the most robust option as it maintained the most consistent performance regardless of fractionation of the selenium species. Kinetic studies and equilibrium isotherms were completed and effectively modeled using pseudo-second order kinetics and Langmuir adsorption theory, making it the first comprehensive systematic study of neat n-Al2O3 and AICB for selenium adsorption. pH significantly impacted adsorption due to changes in the adsorbent surface charge; increasing pH corresponded with decreasing adsorbent performance, beginning at approximately pH 6.5-7 for AICB. The trend in performance due to the effect of pH indicated that selenate binds to the amine group in chitosan, as suggested by other studies. In addition, increasing background sulfate concentration was found to negatively impact adsorption efficacy for both selenite, and more significantly, selenate, as sulfate is known to compete with selenium oxyanions due to their similar structures. The results indicate that, in order to maintain consistent removal in more realistic systems, a pre-treatment process to manage sulfate will be necessary as indicated for other adsorbents implemented for selenium adsorption in aqueous systems.