Is replacing missing values of PM2.5 constituents with estimates using machine learning better for source apportionment than exclusion or median replacement?

East Asian countries have been conducting source apportionment of fine particulate matter (PM2.5) by applying positive matrix factorization (PMF) to hourly constituent concentrations. However, some of the constituent data from the supersites in South Korea was missing due to instrument maintenance and calibration. Conventional preprocessing of missing values, such as exclusion or median replacement, causes biases in the estimated source contributions by changing the PMF input. Machine learning (ML) can estimate the missing values by training on constituent data, meteorological data, and gaseous pollutants. Complete data from the Seoul Supersite in 2018 was taken, and a random 20% was set as missing. PMF was performed by replacing missing values with estimates. Percent errors of the source contributions were calculated compared to those estimated from complete data. Missing values were estimated using a random forest analysis. Estimation accuracy (r2) was as high as 0.874 for missing carbon species and low at 0.631 when ionic species and trace elements were missing. For the seven highest contributing sources, replacing the missing values of carbon species with estimates minimized the percent errors to 2.0% on average. However, replacing the missing values of the other chemical species with estimates increased the percent errors to more than 9.7% on average. Percent errors were maximal at 37% on average when missing values of ionic species and trace elements were replaced with estimates. Missing values, except for carbon species, need to be excluded. This approach reduced the percent errors to 7.4% on average, which was lower than those due to median replacement. Our results show that reducing the biases in source apportionment is possible by replacing the missing values of carbon species with estimates. To improve the biases due to missing values of the other chemical species, the estimation accuracy of the ML needs to be improved.

Borohydride and halide dual-substituted lithium argyrodites.

Solid electrolyte is a crucial component of all-solid-state batteries, with sulphide solid electrolytes such as lithium argyrodite being closest to commercialization due to their high ionic conductivity and formability. In this study, borohydride/halide dual-substituted argyrodite-type electrolytes, Li7-α-ßPS6-α-ß(BH4)αXß (X = Cl, Br, I; α + ß ≤ 1.8), have been synthesized using a two-step ball-milling method without post-annealing. Among the various compositions, Li5.35PS4.35(BH4)1.15Cl0.5 exhibits the highest ionic conductivity of 16.4 mS cm-1 at 25 °C when cold-pressed, which further improves to 26.1 mS cm-1 after low temperature sintering. The enhanced conductivity can be attributed to the increased number of Li vacancies resulting from increased BH4 and halide occupancy and site disorder. Li symmetric cells with Li5.35PS4.35(BH4)1.15Cl0.5 demonstrate stable Li plating and stripping cycling for over 2,000 hours at 1 mA cm-2, along with a high critical current density of 2.1 mA cm-2. An all-solid-state battery prepared using Li5.35PS4.35(BH4)1.15Cl0.5 as the electrolyte and pure Li as the anode exhibits an initial coulombic efficiency of 86.4%. Although these electrolytes have limited thermal stability, it shows a wide compositional range while maintaining high ionic conductivity.

Effects of host plant on the development and reproduction of Agrotis ipsilon (Lepidoptera: Noctuidae) on horticultural crops.

One of cosmopolitan pest, Agrotis ipsilon (Lepidoptera: Noctuidae), causes serious economic damages in horticultural crops. This pest is difficult to manage and causes irreversible damage because its larvae stay in the ground at day and cut the plant stems at night. Thus, this study compared the host fitness of A. ipsilon among nine major horticultural crops in Korea. Among the nine crops, the population of A. ipsilon failed to complete its development in spinach, cucumber, melon, and kidney bean. The host effects on development and reproduction of A. ipsilon were further investigated in the remained five crops (i.e., napa cabbage, soybean, perilla, corn, and pepper). Host plants significantly (P < 0.05) affected the development-related factors (i.e., developmental time, survivorship, and weight) of A. ipsilon eggs, larvae, and pupae. They also affected the adult reproduction-related factors including preoviposition period, oviposition period and number, and longevity except for the prepupa stage. A positive relationship was found between biological factors (i.e., development- and reproduction-related factors). Among the nine crops in this study, napa cabbage showed the highest suitability for the A. ipsilon populations. These findings in this study would be helpful to understand the ecology and develop the management tactics of A. ipsilon in horticultural crops.

Predicting latent source-specific PM2.5 pollution from regional sources at unmonitored sites by Bayesian spatial multivariate receptor modeling.

Fine particulate matter (PM2.5) has been a pollutant of main interest globally for more than two decades, owing to its well-known adverse health effects. For developing effective management strategies for PM2.5, it is vital to identify its major sources and quantify how much they contribute to ambient PM2.5 concentrations. With the expanded monitoring efforts established during recent decades in Korea, speciated PM2.5 data needed for source apportionment of PM2.5 are now available for multiple sites (cities). However, many cities in Korea still do not have any speciated PM2.5 monitoring station, although quantification of source contributions for those cities is in great need. While there have been many PM2.5 source apportionment studies throughout the world for several decades based on monitoring data collected from receptor site(s), none of those receptor-oriented studies could predict unobserved source contributions at unmonitored sites. This study predicts source contributions of PM2.5 at unmonitored locations using a recently developed novel spatial multivariate receptor modeling (BSMRM) approach, which incorporates spatial correlation in data into modeling and estimation for spatial prediction of latent source contributions. The validity of BSMRM results is also assessed based on the data from a test site (city), not used in model development and estimation.

Computational design of novel MAX phase alloys as potential hydrogen storage media combining first principles and cluster expansion methods.

Finding a suitable material for hydrogen storage under ambient atmospheric conditions is challenging for material scientists and chemists. In this work, using a first principles based cluster expansion approach, the hydrogen storage capacity of the Ti2AC (A = Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, and Zn) MAX phase and its alloys was studied. We found that hydrogen is energetically stable in Ti-A layers in which the tetrahedral site consisting of one A atom and three Ti atoms is energetically more favorable for hydrogen adsorption than other sites in the Ti-A layer. Ti2CuC has the highest hydrogen adsorption energy than other Ti2AC phases. We find that the 83.33% Cu doped Ti2AlxCu1-xC alloy structure is both energetically and dynamically stable and can store 3.66 wt% hydrogen under ambient atmospheric conditions, which is higher than that stored by both Ti2AlC and Ti2CuC phases. These findings indicate that the hydrogen capacity of the MAX phase can be significantly improved by doping an appropriate atom species.

Effects of Lymantria dispar multiple nucleopolyhedrovirus and Bacillus thuringiensis var. kurstaki on different larval instars of Lymantria dispar asiatica.

Outbreaks of Lymantria dispar asiatica (the Asian spongy moth; Lepidoptera: Erebidae) occur sporadically, causing widespread damage to forest and fruit trees. Owing to the development of pesticide resistance and environmental contamination, biopesticides, including L. dispar multiple nucleopolyhedrovirus (LdMNPV) and Bacillus thuringiensis var. kurstaki (Btk), can significantly contribute to controlling overall larval stage of this species. Although both pathogens are highly effective at the larval stage, their effects on different instar stages have not been investigated. In this study, we analyzed the mortality and lethality in different L. dispar asiatica instars exposed to single or combined pathogen treatments. Treatments with low or medium LdMNPV concentrations induced lower mortality and had higher LT50 values at the 4th and 5th instars compared with other instars, whereas high LdMNPV treatments induced high mortality in all instars, with higher LT50 values at later instars. Treatment with Btk induced a rapid 100% mortality in all instars, with higher LT50 values for the later instars. The combination of LdMNPV and Btk delayed the killing time compared with the effects of single treatments, with the effect being more pronounced in the 1st and 5th instar stage than at other stages at low Btk concentrations. Our findings indicate that the pathogenic effects of LdMNPV and Btk on L. dispar asiatica differ according to larval stage, thereby providing novel insights into enhancing the biological control efficacy of these agents against L. dispar asiatica in the field.

Lithium Superionic Conduction in BH4 -Substituted Thiophosphate Solid Electrolytes.

Compared with conventional liquid electrolytes, solid electrolytes can better improve the safety properties and achieve high-energy-density Li-ion batteries. Sulfide-based solid electrolytes have attracted significant attention owing to their high ionic conductivities, which are comparable to those of their liquid counterparts. Among them, Li thiophosphates, including Li-argyrodites, are widely studied. In this study, Li thiophosphate solid electrolytes containing BH4 - anions are prepared via a simple and fast milling method even without heat treatment. The synthesized materials exhibit a high ionic conductivity of up to 11 mS cm-1 at 25 °C, which is much higher than reported values. To elucidate the mechanism behind, the thiophosphate local structure, whose effect on the ionic conductivity remains unclear to date, is investigated. Raman and solid-state NMR spectroscopies are performed to identify the thiophosphate local structure in the sulfide samples. Based on the analysis results, the ratios of the different thiophosphate units in the prepared electrolyte samples are determined. It is found that the thiophosphate local structure can be varied by changing the amount of LiBH4 and the milling conditions, which significantly impact the ionic conductivity. The all-solid-state cell with the prepared solid electrolyte exhibits superior cycle and rate performances.

Dispersal and oviposition patterns of Lycorma delicatula (Hemiptera: Fulgoridae) during the oviposition period in Ailanthus altissima (Simaroubaceae).

The spotted lanternfly (SLF), Lycorma delicatula (Hemiptera: Fulgoridae), has the potential to become a global pest and is currently expanding its range in the United States. In this study, we investigated the dispersal patterns of SLF in Ailanthus altissima during its oviposition period in South Korea using a fluorescent marking system. Oviposition patterns of SLF were then analyzed by surveying egg masses in A. altissima patches. The recapture rate of fluorescent-marked SLF rapidly decreased to 30% within the first two weeks. During the oviposition period, seven cases of among-patch dispersal of SLF adults were observed. The minimum distance that SLF could have traveled to achieve these among-patch dispersal events ranged from 10 to 1740 m, with most events spanning under 60 m. Also, the number of A. altissima trees on which fluorescent marked SLF were detected increased until September. Based on the egg mass survey, a total of 159 egg masses were detected from 38 out of 247 A. altissima trees. Furthermore, 79.2% of egg masses were located < 2.5 m above the ground. Finally, a generalized linear mixed model showed that tree height and diameter at root collar (DRC) of A. altissima trees had significant effects on the number of egg masses.

Health risk assessment and source apportionment of PM2.5-bound toxic elements in the industrial city of Siheung, Korea.

The emission sources and their health risks of fine particulate matter (PM2.5) in Siheung, Republic of Korea, were investigated as a middle-sized industrial city. To identify the PM2.5 sources with error estimation, a positive matrix factorization model was conducted using daily mean speciated data from November 16, 2019, to October 2, 2020 (95 samples, 22 chemical species). As a result, 10 sources were identified: secondary nitrate (24.3%), secondary sulfate (18.8%), traffic (18.8%), combustion for heating (12.6%), biomass burning (11.8%), coal combustion (3.6%), heavy oil industry (1.8%), smelting industry (4.0%), sea salts (2.7%), and soil (1.7%). Based on the source apportionment results, health risks by inhalation of PM2.5 were assessed for each source using the concentration of toxic elements portioned. The estimated cumulative carcinogenic health risks from the coal combustion, heavy oil industry, and traffic sources exceeded the benchmark, 1E-06. Similarly, carcinogenic health risks from exposure to As and Cr exceeded 1E-05 and 1E-06, respectively, needing a risk reduction plan. The non-carcinogenic risk was smaller than the hazard index of one, implying low potential for adverse health effects. The probable locations of sources with relatively higher carcinogenic risks were tracked. In this study, health risk assessment was performed on the elements for which mass concentration and toxicity information were available; however, future research needs to reflect the toxicity of organic compounds, elemental carbon, and PM2.5 itself.

Metastable hexagonal close-packed palladium hydride in liquid cell TEM.

Metastable phases-kinetically favoured structures-are ubiquitous in nature1,2. Rather than forming thermodynamically stable ground-state structures, crystals grown from high-energy precursors often initially adopt metastable structures depending on the initial conditions, such as temperature, pressure or crystal size1,3,4. As the crystals grow further, they typically undergo a series of transformations from metastable phases to lower-energy and ultimately energetically stable phases1,3,4. Metastable phases sometimes exhibit superior physicochemical properties and, hence, the discovery and synthesis of new metastable phases are promising avenues for innovations in materials science1,5. However, the search for metastable materials has mainly been heuristic, performed on the basis of experiences, intuition or even speculative predictions, namely 'rules of thumb'. This limitation necessitates the advent of a new paradigm to discover new metastable phases based on rational design. Such a design rule is embodied in the discovery of a metastable hexagonal close-packed (hcp) palladium hydride (PdHx) synthesized in a liquid cell transmission electron microscope. The metastable hcp structure is stabilized through a unique interplay between the precursor concentrations in the solution: a sufficient supply of hydrogen (H) favours the hcp structure on the subnanometre scale, and an insufficient supply of Pd inhibits further growth and subsequent transition towards the thermodynamically stable face-centred cubic structure. These findings provide thermodynamic insights into metastability engineering strategies that can be deployed to discover new metastable phases.

Valorization of petroleum refinery oil sludges via anaerobic co-digestion with food waste and swine manure.

Valorization of oil sludge has been gaining attention to improve the sustainability of the petroleum industry. This study aimed to assess the possibility of anaerobic co-digestion of oil scum and secondary sludge with food waste (or swine manure). Oil scum and secondary sludge were obtained from a wastewater treatment plant (WWTP) of a petrochemical plant. Physicochemical properties, hazardous materials, and microbial community were characterized and biochemical methane potential was performed by a simplex-lattice mixture design. More than 87% (wet wt.) of the oil scum consisted of total petroleum hydrocarbons (TPHs) (21,762 mg/L) that are difficult to be degraded by anaerobes. The secondary sludge showed low TPHs (5 mg/L) and a bacterial community similar to that of municipal WWTPs. The heavy metal (Cu, As, Cr, Ni, Mn, Zn, and V) concentrations in the oil scum and secondary sludge were similar (20-600 mg/L). The maximum methane potentials of the oil sludge and secondary sludges were 20 ± 2 and 56 ± 3 mL CH4/g-volatile solid, respectively. The co-digestion with food waste or swine manure led to a synergy effect on methane production of the co-digestion substrate (10-40% increase compared to the calculated value; v/v) by balancing the C/N ratio. Due to the high TPH contents, oil scum is not appropriate for co-digestion. The co-digestion of secondary sludge with food waste and/or swine manure is recommended. It is necessary to consider whether the concentration of heavy metals is at a level that inhibits the anaerobic co-digestion depending on the operating conditions such as mixing ratios and solid contents.

Sources of airborne particulate matter-bound metals and spatial-seasonal variability of health risk potentials in four large cities, South Korea.

Fifteen airborne particulate matter-bound metals were analyzed at 14 sites in four large cities (Seoul, Incheon, Busan, Daegu) in South Korea, between August 2013 and June 2017. Among the seven sources resolved by positive matrix factorization, soil dust and marine aerosol accounted for the largest and second largest portions in the three cities; however, in Seoul, soil dust and traffic occupied the largest and the second largest, respectively. Non-carcinogenic risk assessed by inhalation of eight metals (Cd, Co, Ni, Pb, As, Al, Mn, and V) was greater than the hazard index (HI) of 1 at four sites located at or near the industrial complexes. Cumulative incremental lifetime cancer risk (ILCR) due to exposure to five metals (Cd, Co, Ni, Pb, and As) exceeded the 10-6 cancer benchmark at 14 sites and 10-5 at six sites, which includes four sites with HI greater than 1. The largest contributor to ILCR was coal combustion in Seoul, Incheon, and Daegu, and industry sources in Busan. Moreover, industry sources were the largest contributors to non-carcinogenic risk in Seoul, Busan, and Daegu, and soil dust was in Incheon. Incheon had the highest HI in spring because of the higher contribution of soil dust sources than in other seasons. The higher ILCR in Incheon in spring and winter and higher ILCR and HI in Daegu in autumn were mainly due to the influence of industry or coal combustion sources. Statistically significant differences in the ILCR and HI values among the sampling sites in Busan and Daegu resulted from the higher contribution of industry sources at a certain site in the respective city.

Design of V-Substituted TiFe-Based Alloy for Target Pressure Range and Easy Activation.

Titanium iron (TiFe) alloy is a room-temperature hydrogen-storage material, and it absorbs hydrogen via a two-step process to form TiFeH and then TiFeH2. The effect of V addition in TiFe alloy was recently elucidated. The V substitution for Ti sublattice lowers P2/P1 ratio, where P1 and P2 are the equilibrium plateau pressure for TiFe/TiFeH and TiFeH/TiFeH2, respectively, and thus restricts the two-step hydrogenation within a narrow pressure range. The focus of the present investigation was to optimize the V content such that maximum usable storage capacity can be achieved for the target pressure range: 1 MPa for absorption and 0.1 MPa for desorption. The effect of V substitution at selective Ti or Fe sublattices was closely analyzed, and the alloy composition Ti46Fe47.5V6.5 displayed the best performance with ca. 1.5 wt.% of usable capacity within the target pressure range. At the same time, another issue in TiFe-based alloys, which is a difficulty in activation at room temperature, was solved by Ce addition. It was shown that 3 wt.% Ce dispersion in TiFe alloy imparted to it easy room-temperature (RT) activation properties.

Effects of Dangguixu-san in patients with acute lateral ankle sprain: a randomized controlled trial.

BACKGROUND: Dangguixu-san (DS), a herbal extract, is widely used in Korean medicine to treat pain and swelling caused by ankle sprain. However, there is insufficient evidence regarding the effects of DS on ankle sprains. Accordingly, we assessed the efficacy and safety of DS for the treatment of acute lateral ankle sprain (ALAS). METHODS: This study was a multicenter (two Korean hospitals), randomized, double-blind, placebo-controlled, parallel-arm clinical trial with a 1:1 allocation ratio that included a per-protocol analysis and sub-analysis based on symptom severity. Forty-eight participants (n = 28 at Semyung University Korean Medicine Hospital in Chungju; n = 20 at DongShin University Gwangju Korean Medicine Hospital) with grade I or II ALAS that occurred within 72 h before enrollment were randomized to a DS (n = 24) or placebo (n = 24) group. Both groups received acupuncture treatment once daily for 5 consecutive days and the trial medication (DS/placebo capsule) three times a day for 7 consecutive days. Primary (visual analog scale [VAS] scores for pain) and secondary (Foot and Ankle Outcome Scores [FAOS], edema, and European Quality of Life Five-Dimension-Five-Level Scale [EQ-5D-5L] scores) outcome measures were recorded at baseline (week 0), the end of the intervention (week 1), and 4 weeks after treatment completion (week 5). RESULTS: Forty-six participants completed the trial (n = 23 each). Changes in VAS scores, FAOS Symptom/Rigidity, and FAOS Ache from week 1 to week 5 showed significant differences between the two groups. Sub-analyses showed significant differences in changes of FAOS Ache (week 0 to week 5) and VAS scores, total FAOS, and EQ-5D-5L scores (week 1 to week 5) between the two subgroups (grade II). There were no adverse events and significant negative changes in clinical laboratory parameters in both groups. CONCLUSIONS: Overall, the results of this study are in favor of DS combined with acupuncture and suggest that DS combined with acupuncture is a safe treatment with positive long-term effects in terms of pain reduction and symptom alleviation in patients with grade I or II ALAS. TRIAL REGISTRATION: Clinical Research Information Service KCT0002374 . Registered on July 11, 2017; retrospectively registered.

Evaluation of silver nanoparticles (AgNPs) penetration through a clay liner in landfills.

Most products containing engineered nanomaterials are disposed at landfills in the final stage of their lifecycle. This study aims to assess landfill liners as a final barrier of disposed silver nanoparticles (AgNPs). Sorption and transport of AgNPs were investigated in the laboratory-scale simulation of landfill liner conditions. Field soil (silt loam) and bentonite were tested in batch sorption experiments respectively. To test transportation, 3 cm thick mixture of the field soil and the bentonite constituted the porous media to meet the criteria for compacted clay liner of landfill. Mathematical modeling in the experimental and actual landfill conditions was also conducted. The results demonstrated considerable extent of sorption by both types of sorbents. The breakthrough of AgNPs was not observed for 200 days (over 20 pore volume). In general, the experimental results indicated that AgNPs cannot easily pass through the landfill clay liner under present standards. Modeling results also showed that AgNPs could be blocked effectively. Although long-term tests are still required, these results clearly show resistance to current sanitary landfill liners against AgNP penetration. As the trial to assess the safety of landfills against AgNP migration, this work provides insights into the fate and transport of nanomaterials in the landfill environment.

Uncertainty-based concentration estimation of chlortetracycline antibiotics in swine farms and risk probability assessment for agricultural application of manure.

Consideration of livestock farming practices is necessary for the reliable prediction of veterinary antibiotics concentrations in livestock manure and soil and characterization of their ecological risks. This study aims to predict concentrations of chlortetracycline (CTC) generated from slurry pit and evaluate its ecological risk in soil based on the European Medicine Agency guidelines by considering slurry pit farm practices such as cleaning water volume and those uncertainties. Additionally, sensitivity analysis was conducted on the exposure estimation of CTC in soil employing the Monte Carlo simulation. The predicted environmental concentrations of CTC in the slurry pit and soil were in a range of 0.54-5.64 mg/kgmanure and 3.42-67.59 µg/kgsoil, respectively, for a 90 % confidence level. The predicted ranges included the measured values reported in previous studies. The probability of risk quotient (RQ) exceeding one was estimated at 9.3 % based on the Monte Carlo simulation. The four most influential factors on the exposure to CTC in soil were identified as nitrogen in fertilizer/compost, cleaning water volume, ratio of sick pigs requiring antibiotics, and pit emptying cycles. The results indicate that the ecological risk of CTC in the soil is possible and can be controlled by slurry pit farm practices.

Structural Diversity and Trends in Properties of an Array of Hydrogen-Rich Ammonium Metal Borohydrides.

Metal borohydrides are a fascinating and continuously expanding class of materials, showing promising applications within many different fields of research. This study presents 17 derivatives of the hydrogen-rich ammonium borohydride, NH4BH4, which all exhibit high gravimetric hydrogen densities (>9.2 wt % of H2). A detailed insight into the crystal structures combining X-ray diffraction and density functional theory calculations exposes an intriguing structural variety ranging from three-dimensional (3D) frameworks, 2D-layered, and 1D-chainlike structures to structures built from isolated complex anions, in all cases containing NH4+ countercations. Dihydrogen interactions between complex NH4+ and BH4- ions contribute to the structural diversity and flexibility, while inducing an inherent instability facilitating hydrogen release. The thermal stability of the ammonium metal borohydrides, as a function of a range of structural properties, is analyzed in detail. The Pauling electronegativity of the metal, the structural dimensionality, the dihydrogen bond length, the relative amount of NH4+ to BH4-, and the nearest coordination sphere of NH4+ are among the most important factors. Hydrogen release usually occurs in three steps, involving new intermediate compounds, observed as crystalline, polymeric, and amorphous materials. This research provides new opportunities for the design and tailoring of novel functional materials with interesting properties.

Ammonium-Ammonia Complexes, N2H7+, in Ammonium closo-Borate Ammines: Synthesis, Structure, and Properties.

Metal closo-borates have recently received significant attention due to their potential applications as solid-state ionic conductors. Here, the synthesis, crystal structures, and properties of (NH4)2B10H10·xNH3 (x = 1/2, 1 (α and ß)) and (NH4)2B12H12·xNH3 (x = 1 and 2) are reported. In situ synchrotron radiation powder X-ray diffraction allows for the investigation of structural changes as a function of temperature. The structures contain the complex cation N2H7+, which is rarely observed in solid materials, but can be important for proton conductivity. The structures are optimized by density functional theory (DFT) calculations to validate the structural models and provide detailed information about the hydrogen positions. Furthermore, the hydrogen dynamics of the complex cation N2H7+ are studied by molecular dynamics simulations, which reveals several events of a proton transfer within the N2H7+ units. The thermal properties are investigated by thermogravimetry and differential scanning calorimetry coupled with mass spectrometry, revealing that NH3 is released stepwise, which results in the formation of (NH4)2BnHn (n = 10 and 12) during heating. The proton conductivity of (NH4)2B12H12·xNH3 (x = 1 and 2) determined by electrochemical impedance spectroscopy is low but orders of magnitude higher than that of pristine (NH4)2B12H12. The thermal stability of the complex cation N2H7+ is high, up to 170 °C, which may provide new possible applications of these proton-rich materials.

Assessment on landfill liners as the barrier against C60 nanoparticles.

Owing to the increasing usage of nanomaterials, it is imperative to assess their potential impacts on natural systems, and in particular, investigate if existing barriers can prevent nanomaterial emission in landfills because they will be disposed in landfills at the end of their useful lives. This study inspected the behavior of colloidal fullerene (nC60) in and around landfill liner materials. Sorption isotherm experiments using either natural soil or high density polyethylene geomembrane as sorbents showed that nC60 was readily removed by sorption to soil and precipitation, while there was no sorption to geomembrane. To investigate transport through soil, nC60 was injected into columns of compacted soil layers with a thickness of 3.3-4.2 cm and hydraulic conductivity <1 × 10-7 cm/s. The nanoparticles rarely passed through the layers owing to self-aggregation and/or screening by the soil layer. When they were detected in the effluent, breakthrough curves of an extraordinary shape were produced, which is presumably attributed to surface modification of collectors by deposited nC60. However, simulation using the obtained mass transport parameters showed that it is unlikely that nC60 from disposed C60-containing products would overcome compacted clay liners; therefore, its migration to the ambient environment would be negligible.

Ammine Lanthanum and Cerium Borohydrides, M(BH4)3·nNH3; Trends in Synthesis, Structures, and Thermal Properties.

Ammine metal borohydrides show potential for solid-state hydrogen storage and can be tailored toward hydrogen release at low temperatures. Here, we report the synthesis and structural characterization of seven new ammine metal borohydrides, M(BH4)3·nNH3, M = La (n = 6, 4, or 3) or Ce (n = 6, 5, 4, or 3). The two compounds with n = 6 are isostructural and have new orthorhombic structure types (space group P21212) built from cationic complexes, [M(NH3)6(BH4)2]+, and are charge balanced by BH4-. The structure of Ce(BH4)3·5NH3 is orthorhombic (space group C2221) and is built from cationic complexes, [Ce(NH3)5(BH4)2]+, and charge balanced by BH4-. These are rare examples of borohydride complexes acting both as a ligand and as a counterion in the same compound. The structures of M(BH4)3·4NH3 are monoclinic (space group C2), built from neutral molecular complexes of [M(NH3)4(BH4)3]. The new compositions, M(BH4)3·3NH3 (M = La, Ce), among ammine metal borohydrides, are orthorhombic (space group Pna21), containing molecular complexes of [M(NH3)3(BH4)3]. A revised structural model for A(BH4)3·5NH3 (A = Y, Gd, Dy) is presented, and the previously reported composition A(BH4)3·4NH3 (A = Y, La, Gd, Dy) is proposed in fact to be M(BH4)3·3NH3 along with a new structural model. The temperature-dependent structural properties and decomposition are investigated by in situ synchrotron radiation powder X-ray diffraction in vacuum and argon atmosphere and by thermal analysis combined with mass spectrometry. The compounds with n = 6, 5, and 4 mainly release ammonia at low temperatures, while hydrogen evolution occurs for M(BH4)3·3NH3 (M = La, Ce). Gas-release temperatures and gas composition from these compounds depend on the physical conditions and on the relative stability of M(BH4)3·nNH3 and M(BH4)3.