Recent studies have shown that engineered nanoparticles (ENPs) are incorporated into toner powder used in printing equipment and released during their use. Thus, understanding the functional and structural composition and potential synergistic effects of this complex aerosol and released gaseous co-pollutants is critical in assessing their potential toxicological implications and risks. In this study, toner powder and PEPs were thoroughly examined for functional and molecular composition of the organic fraction and the concentration profile of 16 Environmental Protection Agency (EPA)-priority polycyclic aromatic hydrocarbons (PAH) using state of the art analytical methods. Results show significant differences in abundance of non-exchangeable organic hydrogen of toner powder and PEPs, with a stronger aromatic spectral signature in PEPs. Changes in structural composition of PEPs are indicative of radical additions and free-radical polymerization favored by catalytic reactions, resulting in formation of functionalized organic species. Particularly, accumulation of aromatic carbons with strong styrene-like molecular signatures on PEPs is associated with formation of semivolatile heavier aromatic species (i.e., PAHs). Further, the transformation of low molecular weight PAHs in the toner powder to high molecular weight PAHs in PEPs was documented and quantified. This may be a result of synergistic effects from catalytic metal/metal oxide ENPs incorporated into the toner and the presence/release of semi-volatile organic species (SVOCs). The presence of known carcinogenic PAHs on PEPs raises public health concerns and warrants further toxicological assessment.
Urban development has driven extensive modification of the global landscape. This shift in land use and land cover alters ecological functioning, and thereby affects sustainable management agendas. Urbanization fundamentally reshapes the soils that underlay landscapes, and throughout the soil profile, extends impacts of urbanization far below the landscape surface. The impacts of urbanization on deeper soils that are beyond the reach of regular land management are largely unknown, and validation of general theories of convergent ecosystem properties are thwarted by a dearth of both level of measurement effort and the substantial heterogeneity in soils and urban landscapes. Here, we examined two soil properties with strong links to ecological functioning-carbon and mineral-fraction particle size-measured in urban soils, and compared them to their pre-urbanization conditions across a continental gradient encompassing global soil diversity. We hypothesized that urbanization drove convergence of soils properties from heterogeneous pre-urban conditions towards homogeneous urban conditions. Based on our observations, we confirm the hypothesis. Both soil carbon and particle size converged toward an intermediate value in the full data distribution, from pre-urban to urban conditions. These outcomes in urban soils were observed to uniformly be fine textured soils with overall lower carbon content. Although these properties are desirable for supporting urban infrastructure (e.g. buildings, pipes), they constrain the potential to render ecosystem services. Since soil profile texture and carbon content were convergent and observed across 11 cities, we suggest that these property profiles can be used as a universal urban soil profile to: 1) provide a clear prediction for how urbanization will shift soil properties from pre-urban conditions, 2) facilitate the adoption of commonly-accepted soil profiles for process models, and 3) offer a reference point to test against urban management strategies and how they impact soil resources.
Abstract Uncontrolled overland flow drives flooding, erosion, and contaminant transport, with the severity of these outcomes often amplified in urban areas. In pervious media such as urban soils, overland flow is initiated via either infiltration‐excess (where precipitation rate exceeds infiltration capacity) or saturation‐excess (when precipitation volume exceeds soil profile storage) mechanisms. These processes call for different management strategies, making it important for municipalities to discern between them. In this study, we derived a generalized one‐dimensional model that distinguishes between infiltration‐excess overland flow (IEOF) and saturation‐excess overland flow (SEOF) using Green–Ampt infiltration concepts. Next, we applied this model to estimate overland flow generation from pervious areas in 11 U.S. cities. We used rainfall forcing that represented low‐ and high‐intensity events and compared responses among measured urban versus predevelopment reference soil hydraulic properties. The derivation showed that the propensity for IEOF versus SEOF is related to the equivalence between two nondimensional ratios: (a) precipitation rate to depth‐weighted hydraulic conductivity and (b) depth of soil profile restrictive layer to soil capillary potential. Across all cities, reference soil profiles were associated with greater IEOF for the high‐intensity set of storms, and urbanized soil profiles tended towards production of SEOF during the lower intensity set of storms. Urban soils produced more cumulative overland flow as a fraction of cumulative precipitation than did reference soils, particularly under conditions associated with SEOF. These results will assist cities in identifying the type and extent of interventions needed to manage storm water produced from pervious areas.