Evaluation of airborne particulates and associated metals originating from steel slag applied to rural unpaved roads.

Various metals have toxic effects by the inhalation route, and electric arc furnace (EAF) steel slag is known to contain metals with a potential for toxicity to humans. In some states, EAF slag is applied to unpaved (gravel) roads as a low-cost supplement to limestone and other crushed stone, where it may be a public health concern for the local population. This study compared the mass of selected metals in the PM10 size fraction of fugitive dust from roads where slag was applied to metals in fugitive dust where slag was not applied. Manganese, designated by the EPA as a hazardous air pollutant (HAP) and one of the primary metals of concern in the slag, was 1.3 times more concentrated in the PM10 fraction from the slag-covered roads as compared to the PM10 fraction from the non-slag-covered roads, but that increase was not significant (p = 0.26). Other metals detected in the airborne dust from both slag-covered and non-slag-covered roads that are also designated as HAPs are antimony, arsenic, chromium, cobalt, lead, nickel, and selenium. In addition, hourly sampling of PM10 and metals in the PM10 fraction was conducted at one of the sample locations where slag had been applied to the road. Manganese mass in the PM10 was positively correlated (Spearman r = 0.86) with the particulate mass in the PM10. Wind direction and the interaction of traffic and wind direction were found to be statistically significant factors affecting manganese concentrations in the fugitive emissions from the road to which EAF slag had been applied. This research demonstrated that application of steel slag can result in elevated levels of manganese in the airborne dust generated by vehicular traffic on the unpaved roadway.

Intramolecular [2 + 2] Photocycloaddition of Altrenogest: Confirmation of Product Structure, Theoretical Mechanistic Insight, and Bioactivity Assessment.

While studying the environmental fate of potent endocrine-active steroid hormones, we observed the formation of an intramolecular [2 + 2] photocycloaddition product (2) with a novel hexacyclic ring system following the photolysis of altrenogest (1). The structure and absolute configuration were established by X-ray diffraction analysis. Theoretical computations identified a barrierless two-step cyclization mechanism for the formation of 2 upon photoexcitation. 2 exhibited progesterone, estrogen, androgen, and pregnane X receptor activity, albeit generally with reduced potency relative to 1.

Environmental photochemistry of dienogest: phototransformation to estrogenic products and increased environmental persistence via reversible photohydration.

Potent trienone and dienone steroid hormones undergo a coupled photohydration (in light)-thermal dehydration (in dark) cycle that ultimately increases their environmental persistence. Here, we studied the photolysis of dienogest, a dienone progestin prescribed as a next-generation oral contraceptive, and used high resolution mass spectrometry and both 1D and 2D nuclear magnetic resonance spectroscopy to identify its phototransformation products. Dienogest undergoes rapid direct photolysis (t1/2 ∼ 1-10 min), forming complex photoproduct mixtures across the pH range examined (pH 2 to 7). Identified products include three photohydrates that account for ∼80% of the converted mass at pH 7 and revert back to parent dienogest in the absence of light. Notably, we also identified two estrogenic compounds produced via the A-ring aromatization of dienogest, evidence for a photochemically-induced increase in estrogenic activity in product mixtures. These results imply that dienogest will undergo complete and facile photolytic transformation in sunlit surface water, yet exhibit greater environmental persistence than might be anticipated by inspection of kinetic rates. Photoproduct mixtures also include transformation products with different nuclear receptor binding capabilities than the parent compound dienogest. These outcomes reveal a dynamic fate and biological risk profile for dienogest that must also take into account the composition and endocrine activity of its transformation products. Collectively, this study further illustrates the need for more holistic regulatory, risk assessment, and monitoring approaches for high potency synthetic pharmaceuticals and their bioactive transformation products.

Functionalized polymer-iron oxide hybrid nanofibers: Electrospun filtration devices for metal oxyanion removal.

Via a single-pot electrospinning synthesis, we developed a functionalized polymer-metal oxide nanofiber filter for point of use (POU) water treatment of metal oxyanions (e.g., arsenate and chromate). Polyacrylonitrile (PAN) functionalization was accomplished by inclusion of surface-active, quaternary ammonium salts (QAS) [cetyltrimethylammonium bromide (CTAB) or tetrabutylammonium bromide (TBAB)] that provide strong base ion exchange sites. Embedded iron oxide [ferrihydrite (Fh)] nanoparticles were used for their established role as metal sorbents. We examined the influence of QAS and Fh loading on composite properties, including nanofiber morphology, surface area, surface chemical composition, and the accessibility of embedded nanoparticles to solution. Composite performance was then evaluated using kinetic, isotherm, and pH-edge sorption experiments with arsenate and chromate, and benchmarked to unmodified PAN nanofibers and freely dispersed Fh nanoparticles. We also assessed the long-term stability of QAS in the composite matrix. For composites containing QAS or Fh nanoparticles, increasing QAS/Fh nanoparticle loading generally yielded increasing metal oxyanion uptake. The optimized composite (PAN 7 wt%, Fh 3 wt%, TBAB 1 wt%) exhibited two distinct sites for simultaneous, non-competitive metal binding (i.e., iron oxide sites for arsenate removal via sorption and well-retained QAS sites for chromate removal via ion exchange). Moreover, surface-segregating QAS enriched Fh abundance at the nanofiber surface, allowing immobilized nanoparticles to exhibit reactivity comparable to that of unsupported (i.e., suspended or freely dispersed) nanoparticles. To simulate POU application, the optimized composite was tested in a dead-end, flow-through filtration system for arsenate and chromate removal at environmentally relevant concentrations (e.g., µg/L) in both idealized and simulated tap water matrices. Performance trends indicate that dual mechanisms for uptake are maintained in kinetically limited regimes. Although chromate removal via ion exchange is more susceptible to interfering counter-ions, arsenate removal in simulated tap water indicates that ∼130 g of the composite could produce an individual's annual supply of drinking water (assuming an influent contaminated with 100 µg As/L, which is 10 times the current MCL).

Sulfate formation catalyzed by coal fly ash, mineral dust and iron(iii) oxide: variable influence of temperature and light.

Recent atmospheric field and modeling studies have highlighted a lack of understanding of the processes responsible for high levels of sulfate aerosol in the atmosphere, ultimately arising from a dearth of experimental data on such processes. Here we investigated the effect of temperature and simulated solar radiation on the catalytic oxidation of S(iv) to S(vi) (i.e., sulfite to sulfate) in aqueous suspensions of several metal-containing, atmospherically relevant particles including coal fly ash (FA), Arizona test dust (ATD) and an iron oxide (γ-Fe2O3). The effect of temperature and light on S(iv) oxidation was found to be very different for these three samples. For example, in the presence of FA and γ-Fe2O3 the temporal evolution of dissolved Fe(ii) (formed via reductive particle dissolution) correlated with S(iv) oxidation. Accordingly, we propose that S(iv) oxidation in most of these systems initially occurs primarily at the particle surface (i.e., a heterogeneous reaction pathway), although a solution-phase (i.e., homogeneous) catalytic pathway also contributes over later timescales due to the formation and accumulation of dissolved Fe(iii) (generated via oxidation of dissolved Fe(ii) by O2). It is likely that the homogeneous reaction pathway is operative at initial times in the presence of γ-Fe2O3 at 25 °C. In contrast, S(iv) oxidation in the presence of ATD appears to proceed entirely via a heterogeneous reaction, which notably does not lead to any iron dissolution. In fact, the greater overall rate of S(iv) loss in the presence of ATD compared to FA and γ-Fe2O3 suggests that other factors, including greater adsorption of sulfite, transition metal ion (TMI) catalysis by other metal ions (e.g., Ti), or different species of iron in ATD, play a role. Overall these studies suggest that the rate, extent and products of atmospheric S(iv) oxidation can be highly variable and dependent upon the nature of aerosol sources and ambient conditions (e.g., temperature and irradiance). Ultimately, such complexity precludes simple, broadly generalized schemes for this reaction when modeling atmospheric processes involving diverse components of different mineral dust aerosol as well as other metal-containing aerosol.

N-functionalized carbon nanotubes as a source and precursor of N-nitrosodimethylamine: implications for environmental fate, transport, and toxicity.

Hazardous byproducts may be generated during the environmental processing of engineered nanomaterials. Here, we explore the ability of carbon nanotubes with nitrogen-containing surface groups (N-CNTs) to generate N-nitrosodimethylamine (NDMA) during chemical disinfection. Unexpectedly, we observed that commercial N-CNTs with amine, amide, or N-containing polymer (PABS) surface groups are a source of NDMA. As-received powders can leach up to 50 ng of NDMA per mg of N-CNT in aqueous suspension; presumably NDMA originates as a residue from N-CNT manufacturing. Furthermore, reaction of N-CNTs with free chlorine, monochloramine, and ozone generated byproduct NDMA at yields comparable to those reported for natural organic matter. Chlorination also altered N-CNT surface chemistry, with X-ray photoelectron spectroscopy indicating addition of Cl, loss of N, and an increase in surface O. Although these changes can increase N-CNT suspension stability, they do not enhance their acute toxicity in E. coli bioassays above that observed for as-received powders. Notably, however, dechlorination of reacted N-CNTs with sulfite completely suppresses N-CNT toxicity. Collectively, our work demonstrates that N-CNTs are both a source and precursor of NDMA, a probable human carcinogen, while chemical disinfection can produce CNTs exhibiting surface chemistry and environmental behavior distinct from that of native (i.e., as-received) materials.

Chlorinated solvent transformation by palladized zerovalent iron: mechanistic insights from reductant loading studies and solvent kinetic isotope effects.

Palladized nanoscale zerovalent iron (Pd/NZVI) has been utilized for source zone control, yet the reductant responsible for pollutant transformation and the optimal conditions for subsurface application remain poorly understood. Here, trends in Pd/Fe reactivity toward 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) and cis-dichloroethene (cis-DCE) were compared in H2O and D2O batch systems as a function of pH, chlorinated solvent concentration, Pd surface loading, Pd/Fe mass loading, Pd/Fe aging time, and zerovalent iron [Fe(0)] particle size. For Pd/NZVI, the solvent kinetic isotope effect [i.e., kobs(H2O)/kobs(D2O) or SKIE] for 1,1,1,2-TeCA and cis-DCE reduction increased substantially with Pd loading and Pd/NZVI concentration, evidence that multiple pathways exist for chlorinated solvent reduction. At low Pd loadings and Pd/NZVI concentrations with relatively small SKIEs (less than ~5), we propose that modest reactivity enhancements (≤ 10-fold) reflect more efficient electron transfer to 1,1,1,2-TeCA from Fe(0) facilitated by Pd nanodeposits. Much larger SKIEs (e.g., exceeding 100 for cis-DCE) imply the involvement of atomic hydrogen in more reactive systems with high Pd loadings and Pd/NZVI concentrations. Generally, evidence of SKIEs supporting a dominant role for atomic hydrogen was not observed for Pd/Fe prepared from micrometer-sized Fe(0), or for any size of nonpalladized Fe(0). During anaerobic aging of Pd/NZVI, decreases in the SKIE for 1,1,1,2-TeCA reduction suggest that atomic hydrogen will contribute to reactivity for only approximately 1 week after application.

Influence of anionic cosolutes and pH on nanoscale zerovalent iron longevity: time scales and mechanisms of reactivity loss toward 1,1,1,2-tetrachloroethane and Cr(VI).

Nanoscale zerovalent iron (NZVI) was aged over 30 days in suspension (2 g/L) with different anions (chloride, perchlorate, sulfate, carbonate, nitrate), anion concentrations (5, 25, 100 mN), and pH (7, 8). During aging, suspension samples were reacted periodically with 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) and Cr(VI) to determine the time scales and primary mode of NZVI reactivity loss. Rate constants for 1,1,1,2-TeCA reduction in Cl(-), SO(4)(2-), and ClO(4)(-) suspensions decreased by 95% over 1 month but were generally equivalent to one another, invariant of concentration and independent of pH. In contrast, longevity toward 1,1,1,2-TeCA depended upon NO(3)(-) and HCO(3)(-) concentration, with complete reactivity loss over 1 and 14 days, respectively, in 25 mN suspensions. X-ray diffraction suggests that reactivity loss toward 1,1,1,2-TeCA in most systems results from Fe(0) conversion into magnetite, whereas iron carbonate hydroxide formation limits reactivity in HCO(3)(-) suspensions. Markedly different trends in Cr(VI) removal capacity (mg Cr/g NZVI) were observed during aging, typically exhibiting greater longevity and a pronounced pH-dependence. Notably, a strong linear correlation exists between Cr(VI) removal capacities and rates of Fe(II) production measured in the absence of Cr(VI). While Fe(0) availability dictates longevity toward 1,1,1,2-TeCA, this correlation suggests surface-associated Fe(II) species are primarily responsible for Cr(VI) reduction.

Use of dithionite to extend the reactive lifetime of nanoscale zero-valent iron treatment systems.

Nanoscale zero-valent iron (NZVI) represents a promising approach for source zone control, but concerns over its reactive lifetime might limit application. Here, we demonstrate that dithionite (S2O4²â»), a reducing agent for in situ redox manipulation, can restore the reducing capacity of passivated NZVI. Slurries of NZVI were aged in the presence (3 days) and absence (60 days) of dissolved oxygen over a range of pH values (6-8). Upon loss of reactivity toward model pollutants{1,1,1,2-tetrachloroethane, hexavalent chromium [Cr(VI)], nitrobenzene}, aged suspensions were reacted with dithionite, and the composition and reactivity of the dithionite-treated materials were determined. NZVI aging products generally depended on pH and the presence of oxygen, whereas the amount of dithionite influenced the nature and reducing capacity of products generated from reaction with aged NZVI suspensions. Notably, air oxidation at pH ≥ 8 quickly exhausted NZVI reactivity despite preservation of significant Fe(0) in the particle core. Under these conditions, formation of a passive surface layer hindered the complete transformation of NZVI particles into iron(III) oxides, which occurred at lower pH. Reduction of this passive layer by low dithionite concentrations( 1 g/g of NZVI) restored suspension reactivity to levels equal to, and occasionally greater than, that of unaged NZVI. Multiple dithionite additions further improved pollutant removal, allowing at least a 15-fold increase in Cr(VI) removal [∼300 mg of Cr(VI)/g of NZVI] relative to that of as-received NZVI [∼20 mg of Cr(VI)/g of NZVI].

Reactivity of alkyl polyhalides toward granular iron: development of QSARs and reactivity cross correlations for reductive dehalogenation.

Attempts to develop quantitative structure-activity relationships (QSARs) for reductive dehalogenation by granular iron have been hindered by the unavailability of high quality predictor variables, have included relatively few compounds, and on occasion have relied on data lacking internal consistency. We herein investigate the reduction of 24 alkyl polyhalides by granular iron and the better-defined, homogeneous reductants Cr(H(2)O)(6)(2+) and an Fe(II) porphyrin. QSARs were constructed with a new set of computationally derived gas phase homolytic carbon-halogen bond dissociation energies and solvated one-electron reduction potentials determined using a quantum chemistry composite method (G3MP2). Reactivity cross correlations between reductant systems were also developed. Reactivity trends were generally consistent among all reductants and revealed pronounced structural influences. Compounds reduced at C-Br were orders of magnitude more reactive than analogues reduced at C-Cl; the number and identity of α- (Br ∼ Cl > CH(3) > F > H) and ß-substituents (Br > Cl) also influenced reactivity. Nonlinearities encountered during QSAR and cross correlation development suggest that reactions of highly halogenated alkyl polyhalides with granular iron are limited by mass transfer, as supported by estimates of mass transfer coefficients. For species not suspected to exhibit mass transfer limitations, reasonably strong cross correlations and comparable substituent effects are consistent with dissociative electron transfer as the rate-determining step.

Nanogoethite formation from oxidation of Fe(II) sorbed on aluminum oxide: implications for contaminant reduction.

Ferrous iron [Fe(II)] bound to mineral surfaces has been shown to reduce several important groundwater contaminants, but little is known of the nature of the newly formed, insoluble ferric iron [Fe(III)] and whether it influences the heterogeneous contaminant reduction process. To explore how the formation and evolution of the Fe oxidation products influences contaminant reduction, we measured the kinetics of nitrobenzene reduction by Fe(II) sorbed on alpha-Al(2)O(3) while simultaneously characterizing the Fe oxidation product with Mossbauer spectroscopy and electron microscopy. After a brief period of slow kinetics, the onset of nitrobenzene reduction coincided with a change in particle suspension color from white to yellow-ocher due to formation of nanogoethite rods (alpha-FeOOH) from oxidation of sorbed Fe(II). Formation of nanogoethite on the alpha-Al(2)O(3) particles appears to promote the rapid reduction of nitrobenzene. Our results show that nanogoethite crystals can form rapidly by heterogeneous Fe(II) oxidation, and formation of goethite can profoundly influence contaminant reduction rates by Fe(II).

1,1,2,2-tetrachloroethane reactions with OH-, Cr(II), granular iron, and a copper-iron bimetal: insights from product formation and associated carbon isotope fractionation.

Despite widespread implementation of zero-valent iron remediation schemes, the manner and order of chemical bond cleavage in iron-mediated organohalide transformations remains imperfectly understood. We present insights from carbon isotope fractionation for the dehalogenation of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) and 1,1,1-trichloroethane (1,1,1-TCA) by various reactants. Elimination of HCl by OH- gave isotope fractionation in 1,1,2,2-TeCA of Euro = -25.6 per thousand, KIE(c) = 1.02 to 1.03 per carbon center, consistentwith a concerted (E2) mechanism. In contrast, 1,1,1-TCA reduction by Cr(II), Fe(0), and Cu-plated iron (Cu/Fe) resulted in Euro = -13.6 per thousand to -15.8 per thousand indicating the initial involvement of a single C-Cl bond (KIE(c) approximately 1.03). 1,1,2,2-TeCA reduction by Cr(II), Fe(0), and Cu/Fe yielded Euro = -18.7 per thousand, -19.3 per thousand, and -17.0 per thousand, respectively. In the two latter cases, depletion of the minor product TCE by 26 per thousand indicated its formation via nonreductive dehydrohalogenation. The major 1,1,2,2-TeCA reduction products, cis- and trans-DCE, differed by 2.3 per thousand +/- 1.0 per thousand in Cr(II) systems, but were equivalent in Fe(0) and Cu/Fe systems. In contrast, the ratio of cis-DCE to trans-DCE concentration was 2.5 for reduction with Cr(II) and Fe(0), but -3.8 with Cu/Fe. Complementary isotope and concentration data therefore suggest differences in the transition state geometry and/ or reaction intermediates in each reductant system.

Influence of the oxidizing species on the reactivity of iron-based Bimetallic reductants.

Anticipating which pollutants are amenable to treatment by iron-based bimetallic reductants requires an understanding of the mechanism(s) driving pollutant reduction. Here, batch studies with six bimetals (Au/Fe, Co/Fe, Cu/Fe, Ni/ Fe, Pd/Fe, and Pt/Fe) and four oxidants (alkyl polyhalides, vinyl polyhalides, alkynes, and water) explored the influence of the electron acceptor on reductant reactivity. Bimetals exhibited disparate reactivity toward some oxidant classes. For example, Pt/Fe enhanced rates of cis-dichloroethylene reduction, but it inhibited the reduction of several alkyl polyhalides. Moreover, the rate increase for vinyl polyhalide reduction by Ni/Fe (approximately 100-fold) and Pd/Fe (approximately 1000-fold) was far greater than that measured for alkyl polyhalides (approximately 10-fold), and reactivity toward vinyl polyhalides exhibited a more pronounced dependence on Ni and Pd loadings than did reactivity toward alkyl polyhalides. These results suggest that the reactions of alkyl and vinyl polyhalides with iron-based bimetals involve different active reductants. Neither rates of alkyl nor vinyl polyhalide reduction correlated with rates of iron corrosion by water, contrary to expectations if galvanic corrosion was primarily responsible for organohalide reduction. Trends observed for the hydrogenation of 2-butyne did mirror the sequence we identified for 1,1,1-trichloroethane reduction, consistent with a role for atomic hydrogen as the principal electron donor in these two systems.

Exploring the influence of granular iron additives on 1,1,1-trichloroethane reduction.

Bimetallic reductants are frequently more reactive toward organohalides than unamended iron and can also alter product distributions, yet a molecular-level explanation for these phenomena remains elusive. In this study, surface characterization of six iron-based bimetallic reductants (Au/Fe, Co/Fe, Cu/Fe, Ni/Fe, Pd/Fe, and Pt/Fe) revealed that displacement plating produced a non-uniform overlayer of metallic additive on iron. Batch studies demonstrated that not all additives enhanced rates of 1,1,1-trichloroethane (1,1,1-TCA) reduction nor was there any clear periodic trend in the observed reactivity (Ni/Fe approximately Pd/Fe > Cu/Fe > Co/ Fe > Au/Fe approximately Fe > Pt/Fe). Pseudo-first-order rate constants for 1,1,1-TCA reduction (kobs values) did, however, correlate closely with the solubility of atomic hydrogen within each additive. This suggests absorbed atomic hydrogen, rather than galvanic corrosion, is responsible for the enhanced reactivity of bimetallic reductants. In addition, all additives shifted product distributions to favor the combined yield of ethylene plus ethane over 1,1-dichloroethane. In rate-enhancing bimetallic systems, branching ratios between 1,1-dichloroethane and the combination of ethylene and ethane were uniquely dependent on kobs values, indicating an intimate link between rate-determining and product-determining steps. We propose that our results are best explained by an X-philic pathway involving atomic hydrogen with a hydride-like character.

Influence of copper loading and surface coverage on the reactivity of granular iron toward 1,1,1-trichloroethane.

Although iron-based bimetallic reductants offer promise in treating organohalides, the influence of additive mass loading and two-dimensional surface coverage on reductant reactivity has not been fully elucidated. In this study we examine 1,1,1-trichloroethane reduction by Cu/Fe bimetals as a function of Cu loading and surface coverage. Information from a suite of complementary techniques (X-ray photoelectron spectroscopy, Auger electron spectroscopy, and cross-sectional energy-dispersive X-ray spectroscopy) indicates that displacement plating produces a heterogeneous metallic copper overlayer on iron. The dependence of pseudo-first-order rate constants (k(obs) values) for 1,1,1-trichloroethane reduction on Cu loading exhibits two distinct regimes. At Cu loadings less than 1 monolayer equivalent (approximately 10 micromol Cu/g Fe), a pronounced increase in k(obs) is associated with a corresponding increase in the two-dimensional surface coverage of Cu. A weaker dependence of k(obs) on Cu mass is exhibited at loadings in excess of 1 monolayer equivalent, which we ascribe to an increase in the volume of the metallic overlayer. The observed relationship between k(oba) and loading suggests that 1,1,1-trichloroethane reduction occurs on the Cu surface rather than at the interface between the Cu overlayer and the iron substrate.

On the nonlinear relationship between k(obs) and reductant mass loading in iron batch systems.

A first-order relationship between reaction rate and reductant loading is commonly invoked (but rarely verified) for granular iron batch systems. In this study, a linear relationship between the pseudo-first-order rate constant (k(obs)) for polyhalogenated alkane reduction and iron mass loading (rhom) was only obtained when reduction appeared to be mass-transport-limited. For most alkyl polyhalides, a nonlinear relationship was observed under various experimental conditions, causing surface-area-normalized rate constants (k(SA)) to decrease by as much as an order of magnitude with increasing rhom. While a detailed explanation for this nonlinearity remains unclear, the reaction order in rhom (from plots of log(k(obs)) versus log(rhom)) approached unity as the system pH decreased, suggesting that the behavior may be linked to changes in the thickness of a passive oxide overlayer. We obtained strong linear correlations between k(obs) values and the concentration of aqueous iron(ll) generated over a 24 h period in batch systems with that same rhom. Equally strong correlations were obtained when k(obs) was related to the summed concentration of protons and water reduced over an equivalent time interval at that same rhom. Such correlations suggest a possible link between those sites responsible for proton/water reduction and the surface species participating in alkyl polyhalide reduction by granular iron.