This paper shows that synchrotron-based fluorescence and absorption-edge computed microtomographies (CMT) are well-suited for determining the compartmentalization and concentration of metals in hyperaccumulating plant tissues. Fluorescence CMT of intact leaf, stem, and root samples revealed that Ni concentrated in stem and leaf dermal tissues and, together with Mn, in distinct regions associated with the Ca-rich trichomes on the leaf surface of the nickel hyperaccumulator Alyssum murale "Kotodesh". Metal enrichment was also observed within the vascular system of the finer roots, stem, and leaves but absent from the coarser root, which had a well-correlated metal coating. Absorption-edge CMT showed the three-dimensional distribution of the highest metal concentrations and verified that epidermal localization and Ni and Mn co-localization at the trichome base are phenomena that occurred throughout the entire leaf and may contribute significantly to metal detoxification and storage. Ni was also observed in the leaf tips, possibly resulting from release of excess Ni with guttation fluids. These results are consistent with a transport model where Ni is removed from the soil by the finer roots, carried to the leaves through the stem xylem, and distributed throughout the leaf by the veins to the dermal tissues, trichome bases, and in some cases the leaf tips.

Summary• The nickel (Ni) hyperaccumulator Alyssum murale has been developed as a commercial crop for phytoremediation/phytomining Ni from metal-enriched soils. Here, metal co-tolerance, accumulation and localization were investigated for A. murale exposed to metal co-contaminants.• A. murale was irrigated with Ni-enriched nutrient solutions containing basal or elevated concentrations of cobalt (Co) or zinc (Zn). Metal localization and elemental associations were investigated in situ with synchrotron X-ray microfluorescence (SXRF) and computed-microtomography (CMT).• A. murale hyperaccumulated Ni and Co ( > 1000 µg g -1 dry weight) from mixedmetal systems. Zinc was not hyperaccumulated. Elevated Co or Zn concentrations did not alter Ni accumulation or localization. SXRF images showed uniform Ni distribution in leaves and preferential localization of Co near leaf tips/margins. CMT images revealed that leaf epidermal tissue was enriched with Ni but devoid of Co, that Co was localized in the apoplasm of leaf ground tissue and that Co was sequestered on leaf surfaces near the tips/margins.• Cobalt-rich mineral precipitate(s) form on leaves of Co-treated A. murale . Specialized biochemical processes linked with Ni (hyper)tolerance in A. murale do not confer (hyper)tolerance to Co. A. murale relies on a different metal storage mechanism for Co (exocellular sequestration) than for Ni (vacuolar sequestration).

Biodiesel fuels may serve as a partial solution in the search for sustainable energy sources for the transportation sector. However, increased nitrogen oxide (NO x ) emissions are a potentially significant drawback to the use of biodiesel fuels that must be addressed if biodiesel is to gain widespread acceptance. One approach is to identify specific biodiesel fuel properties that minimize NO x formation and use these to produce lower NO x fuel blends. In this work, seven biodiesel fuels were produced from high-erucic rapeseed, olive, palm, coconut, soybean, and fresh and used canola oils, with their chemical composition determined using gas chromatography−mass spectrometry (GC−MS). The fuels were then burned in a single-cylinder directinjection diesel engine and evaluated for both fuel consumption and exhaust emissions of nitrogen oxides, carbon monoxide (CO), unburned hydrocarbons, and particulate matter. While all biodiesels had higher brake-specific nitric oxide (NO) emissions than ultralow sulfur diesel (ULSD) at low engine loads, olive, palm, coconut, and canola biodiesels performed better than ULSD at 50% loading and above. Nitrogen dioxide (NO 2 ), CO, and unburned hydrocarbon emissions were generally lower from the biodiesel fuels than ULSD. Palm biodiesel consistently generated the lowest brake-specific NO x levels of all tested fuels. Statistical analysis of the results showed that higher fuel hydrogen/carbon molar ratios, low polyunsaturation levels, and lower fuel density were all significantly associated with reduced NO emissions in the tested biodiesel fuels but no clear trends were observed for NO 2 . The results suggest that pathways exist for tailoring the fuel properties of biodiesel blends to reduce nitrogen oxide emission compared to current fuels.

The formation of mixed-metal-Al layered double hydroxide (LDH) phases similar to hydrotalcite has been identified as a significant mechanism for immobilization of trace metals in some environmental systems. These precipitate phases become increasingly stable as they age, and their formation may therefore be an important pathway for sequestration of toxic metals in contaminated soils. However, the lack of thermodynamic data for LDH phases makes it difficult to model their behavior in natural systems. In this work, enthalpies of formation for Ni LDH phases with nitrate and sulfate interlayers were determined and compared to recently published data on carbonate interlayer LDHs. Differences in the identity of the anion interlayer resulted in substantial changes in the enthalpies of formation of the LDH phases, in the order of increasing enthalpy carbonate<sulfate<nitrate. Substitution of silica for carbonate resulted in an even more exothermic enthalpy of formation, confirming that silica substitution increases the stability of LDH precipitates. Both mechanical mixture and solid-solution models could be used to predict the thermodynamic properties of the LDH phases. Modeling results based on these thermodynamic data indicated that the formation of LDH phases on soil mineral substrates decreased Ni solubility compared to Ni(OH)2 over pH 5–9 when soluble Al is present in the soil substrate. Over time, both of these precipitate phases will transform to more stable Ni phyllosilicates.