David L. Monts

2,4,6-Trinitrotoluene detection by laser-photofragmentation-laser-induced fluorescence.

Photofragmentation (PF) and subsequent nitric oxide (NO) laser-induced fluorescence (LIF) is being developed to measure the concentration of energetic materials (EMs) in soil and other media. Laser radiation near 226 nm photodissociates gas-phase EM to NO(2), which predissociates into NO that gives an intense luminescence. The EM concentration is inferred from the intensity of the NO fluorescence. We have studied the factors that affect the PF-LIF signal intensity, including the effect of buffer gas on the LIF spectrum of pure NO, the effect of 2,4,6-trinitrotoluene (TNT) pressure on the PF-LIF spectrum, the effect of buffer-gas pressure on the PF-LIF signal intensity of pure TNT, and the effect of temperature on the PF-LIF spectra of pure TNT and of TNT in simulated soil. Heating of the TNT sample above 343 K was found to increase the magnitude of the PF-LIF signal intensity significantly, but also was found to cause physical and chemical changes in the TNT sample. The effects of heating and evacuating on the TNT sample were investigated. TNT concentration calibration curves were obtained for TNT in simulated soil mixtures. The limit of detection of TNT in soil was estimated to be 40 parts in 10(9).

Phytotoxicity of mercury in Indian mustard (Brassica juncea L.).

This study investigated the phytotoxicity of mercury to Indian mustard (Brassica juncea L.). Two common cultivars (Florida Broad Leaf and Long-standing) were grown hydroponically in a mercury-spiked solution. Mercury exhibited a significant phytotoxicity in these two cultivars of Indian mustard at elevated concentrations (>or=2 mg L(-1)). Mercury uptake induced a significant reduction in both biomass and leaf relative water content. Microscopy studies indicated that elevated mercury concentrations in plants significantly changed leaf cellular structure: thickly stained areas surrounding the vascular bundles; decreases in the number of palisade and spongy parenchyma cells; and reduced cell size and clotted depositions. The palisade chloroplasts exhibited decreases in their amounts and starch grains as well as a loss of spindle shape. However, due to high accumulation of mercury in plants, especially in the roots, Indian mustard might be a potential candidate plant for phytofiltration of contaminated water and phytostabilization of mercury-contaminated soils.

Distribution, transformation and bioavailability of trivalent and hexavalent chromium in contaminated soil

The purpose of this study was to investigate solid-phase distribution, transformation, and bioavailability of Cr in Cr(III) and Cr(VI) contaminated soils. The effects of EDTA treatment on solid-phase distribution of Cr in soils were also examined. The results show that Cr in both initially Cr(III)- and Cr(VI)-contaminated soils was mainly present in the organic matter bound fraction. Chromium had similar solid-phase distribution and similar overall binding intensity in both Cr(III)- and Cr(VI)-contaminated soils after a growing season. Transformation between Cr(III) and Cr(VI) took place in both Cr(III)- and Cr(VI)-treated soils. Chromium in the Cr(III)-contaminated soils was mostly present as Cr(III), while Cr in Cr(VI)-treated soils was mainly transformed into Cr(III). About 2% of Cr in native non-treated soils was found as Cr(VI). EDTA treatment increased Cr in soluble and exchangeable fraction in Cr(III)-treated soils. In both Cr(III)- and Cr(VI)-contaminated soils, Cr in oxide bound and organic matter bound

Effects of Zn and Cd accumulation on structural and physiological characteristics of barley plants

The objectives of this study were to identify the structural changes caused by Zn and Cd accumulation in shoots and roots of barley (Hordeum vulgare) plants; and to correlate metal accumulation with anatomical, physiological and morphological changes. Potted plants were exposed to metal treatments of Zn and Cd for 19 and 16 d respectively. Leaves, stems and roots were harvested to identify structural changes and analyze metal accumulation. Barley effectively accumulated Zn (up to 11283 mg kg-1) and Cd (up to 584 mg kg-1) in the shoots. Microscopic structural changes, such as a decrease in intercellular spaces, breakdown of vascular bundles, and shrinkage of palisade and epidermal cells, occurred in leaves, stems and roots of plants treated with high concentrations of Zn. Zinc accumulation also resulted in a significant decrease in water content, fresh weight, dry weight and plant height. Cadmium only caused structural changes in roots at the higher concentrations. Barley plants were able to accumulate significant amounts of Zn and Cd without exhibiting symptoms of phytotoxicity when the metal concentrations were relatively low.

Phytotoxicity and phytoaccumulation of trivalent and hexavalent chromium in brake fern

A recently recognized hyperaccumulator plant, Chinese brake fern (Pteris vittata), has been found to extract very high concentration of arsenic from arsenic-contaminated soil. Chromium usually is a coexisting contaminant with arsenic in most contaminated soils. The potential application of ferns for phytoremediation of chromium(III)- and chromium(VI)-contaminated soils and their phytotoxicity to ferns has not been studied before. In this study, chromium distribution and phytotoxicity at the plant and cellular levels of brake ferns were studied using chemical analyses and scanning electron microscopy. The results show a higher phytotoxicity of Cr from Cr(VI)-contaminated soil to Chinese brake fern than from Cr(III)-contaminated soil. Phytotoxicity symptoms included significant decreases both in fresh biomass weight and relative water content (RWC), and also in leaf chlorosis during the late stage of growing. At higher concentrations (500 mg/kg Cr[VI] and 1,000 mg/kg Cr[III] addition), plants showed reduction in the number of palisade and spongy parenchyma cells in leaves. Compared with other plant species reported for phytoremediation of Cr(VI)-contaminated soil, brake fern took up and accumulated significant amounts of Cr (up to 1,145 mg/kg in shoots and 5,717 mg/kg in roots) and did not die immediately from phytotoxicity. Our study suggests that Chinese brake fern is a potential candidate for phytoremediation of Cr(VI)-contaminated soils, even though plants showed severe phytotoxic symptoms at higher soil Cr concentrations.

Optical Properties of Gaseous 2,4,6-Trinitrotoluene in the Ultraviolet Region

The absorption spectrum of gaseous 2,4,6-trinitrotoluene (TNT) was recorded by conventional absorption spectroscopy (AS) as well as cavity ringdown spectroscopy (CRDS) methods in the spectral regions 195–300 and 225–235 nm, respectively. These spectra were normalized by using the saturated TNT vapor-number density for the measured cell temperature to obtain the absorption cross section of TNT. No spectral features were found in the spectra; this result is consistent with a repulsive electronic excited state of TNT. The temperature dependence of the absorption coefficient of saturated TNT vapor was measured within the temperature range 5–110 °C. The limit of detection of TNT vapor by CRDS is less than 1 ppb. Real-time CRDS measurements of the TNT vapor density at 21 and 37 °C are presented. The TNT evaporation rates were found to be 7 × 108 and 4 × 1010 molecules/cm2 × s at 21 and 37 °C, respectively.

Spectral reflectance and leaf internal structure changes of barley plants due to phytoextraction of zinc and cadmium

The focus of our research is to seek spectral signatures that indicate the impact and content of heavy metals in the leaves and canopies of living plants during the process of phytoremediation. Potted plants of barley (Hordeum vulgare) were grown for 5–6 weeks before being subjected to metal treatments of Zn and Cd. Diffuse reflectance spectra (350–2500 nm) of the plant canopies were collected daily using a portable spectroradiometer throughout the treatment period. Foliar structural changes of Zn‐treated plants included a decrease in intercellular space, palisade and epidermal cell size while Cd‐treated plants displayed fewer structural changes in leaf. Spectral analysis revealed that the band ratios at 1110 nm to that at 810 nm might be used as an indicator of the accumulation of certain metals in plant shoots. Normalized Difference Vegetation Index (NDVI) and leaf‐water‐content indices examined as part of our spectral analysis were not able to distinguish plants treated with different metals. Our ratio index R1110/R810, on the other hand, correlates closely with the magnitude of leaf structural changes. This study suggests that the infrared reflectance spectrum (800–1300 nm) of plant canopy might provide a non‐intrusive monitoring method for the physiological status of plants grown on heavy metal contaminated soil.

Mercury‐induced oxidative stress in Indian mustard (Brassica juncea L.)

Mercury, a potent neurotoxin, is released to the environment in significant amounts by both natural processes and anthropogenic activities. No natural hyperaccumulator plant has been reported for mercury phytoremediation. Few studies have been conducted on the physiological responses of Indian mustard, a higher biomass plant with faster growth rates, to mercury pollution. This study investigated the phytotoxicity of mercury to Indian mustard (Brassica juncea L.) and mercury‐induced oxidative stress in order to examine the potential application of Indian mustard to mercury phytoremediation. Two common cultivars (Florida Broadleaf and Longstanding) of Indian mustard were grown hydroponically in a mercury‐spiked solution. Plant uptake, antioxidative enzymes, peroxides, and lipid peroxidation under mercury stress were investigated. Antioxidant enzymes (catalase, CAT; peroxidase, POD; and superoxide dismutase, SOD) were the most sensitive indices of mercury‐induced oxidative response of Indian mustard plants. Indian mustard effectively generated an enzymatic antioxidant defense system (especially CAT) to scavenge H2O2, resulting in lower H2O2 in shoots with higher mercury concentrations. These two cultivars of Indian mustard demonstrated an efficient metabolic defense and adaptation system to mercury‐induced oxidative stress. A majority of Hg was accumulated in the roots and low translocations of Hg from roots to shoots were found in two cultivars of Indian mustard. Thus Indian mustard might be a potential candidate plant for phytofiltration/phytostabilization of mercury contaminated waters and wastewater.

Effect of Phytoaccumulation of Arsenic and Chromium on Structural and Ultrastructural Changes of Brake Fern (Pteris vittata)

Structural and ultrastructural changes caused by bioaccumulation of As and Cr in brake fern (Pteris vittata), a known arsenic hyperaccumulator, were investigated. Potted plants of brake fern were exposed to metal treatments of As and Cr for three weeks. Leaf, stem and root samples were collected periodically and fixed for LM (Light Microscopy), SEM (Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy) to evaluate anatomical changes. The fresh weights, dry weights, RWC (Relative Water Content) and plant heights were obtained before the brake fern plants were harvested for metal accumulation analysis. The As accumulated mainly in the shoots while Cr accumulated mainly in the roots of the metal-treated plants. Significant changes in the ferns physical characters, including fresh weight, dry weight, RWC, and plant height were observed for only Cr-treated plants but not for As-treated plants. Microscopic studies reveal the Cr accumulation resulted in dehydration and collapse of internal structure of leaves and cellular breakdown of roots. The As-treated plants showed no significant structural changes in leaves, stems and roots compared to control plants. Clotted depositions were observed in roots and stems of plant groups treated with highest concentration of Cr and As when compared to control (T0) group. Our study indicates that Cr has a profound impact on physiology and structure of fern plants. The accumulation of Cr resulted in decrease in growth rate, total biomass and RWC. We believe that brake fern plants can uptake, translocate and sequester As because it caused no significant structural changes in leaves, stems and roots of the plants.

Phytoextraction and Accumulation of Mercury in Three Plant Species: Indian Mustard (Brassica Juncea), Beard Grass (Polypogon monospeliensis), and Chinese Brake Fern (Pteris vittata)

The objective of this research was to screen and search for suitable plant species to phytoextract mercury-contaminated soil. Our effort focused on using some of the known metal-accumulating wild-type plants since no natural plant species with mercury-hyperaccumulat ing properties has yet been identified. Three plant species were evaluated for their uptake efficiency for mercury: Indian mustard (Brassica juncea), beard grass (Polypogon monospeliensis), and Chinese brake fern (Pteris vittata). Four sets of experiments were conducted to evaluate the phytoremediation potential of these three plant species: a pot study with potting mix where mercury was provided daily as HgCl2 solution; experiments with freshly mercury-spiked soil; and a study with aged soils contaminated with different mercury sources (HgCl2, Hg(NO3)2, and HgS). Homemade sunlit chambers were also used to study foliar uptake of Hg from ambient air. Among the three plant species, Chinese brake fern showed the least stress symptoms resulting from mercury exposure and had the highest mercury accumulation. Our results indicate that Chinese brake fern may be a potential candidate for mercury phytoextraction. We found that mercury contamination is biologically available for plant uptake and accumulation, even if the original and predominating mercury form is HgS, and also after multiple phytoremediation cycles.