Joel G. Burken

Distribution and Volatilization of Organic Compounds Following Uptake by Hybrid Poplar Trees

ABSTRACT Hybrid poplar trees were exposed to eleven organic compounds in hydroponic systems. The eleven contaminants were common pollutants with a wide range of physio-chemical properties such as the octanol-water partition coefficient, Henrys constant, vapor pressure, and molecular weight. Contaminants, 14C-labeled, were introduced into the root zone, and contaminant transport and fate were examined. Aqueous concentrations were monitored throughout each experiment as was vapor phase concentrations in the air stream passing over the leaves. At experiment conclusion, plant tissues were oxidized to determine 14C concentrations. The uptake, distribution, and volatilization of these contaminants varied greatly among the 11 contaminants in the study. Uptake and translocation of the contaminants ranged from < 0.3% (of the applied 14C-labeled compound) for 1,2,4-trichlorobenzene to 20% for benzene. Volatile compounds were volatilized from the leaves. Volatilization in the transpiration stream was related to the...

Adsorption of arsenic(V) onto fly ash: a speciation-based approach.

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists in the world. The large volume of coal fly ash produced around the world is a potentially significant anthropogenic source of arsenic. Currently the leaching behavior of arsenic from fly ash is not well understood. Batch methods were used in this study to investigate arsenic leaching using a raw ash, and arsenic adsorption using a clean, washed ash. Experimental results indicated that pH had a significant effect on arsenic leaching or adsorption. Between pH 3 and 7, less arsenic was in the dissolved phase. When pH was less than 3 or greater than 7, increasing amounts of arsenic were leached or desorbed from fly ash. The leaching and adsorption behavior of arsenic was interpreted with the speciation of surface sites and arsenic. In a new approach, a speciation-based model was developed to quantify the arsenic adsorption as a function of pH and surface acidity parameters. This work is important in offering insight into the leaching mechanism of arsenic from coal fly ash, and providing a robust model based upon specific, measurable parameters to quantify arsenic adsorption by other solid media in addition to fly ash.

Phytoremediation of MTBE with Hybrid Poplar Trees

ABSTRACT This research investigates the fate and transport of methyl tert-butyl ether (MTBE) in phytoremediation, particularly the uptake and volatilization of MTBE in lab-scale hydroponic systems. The research reveals that MTBE was taken up by hybrid poplar cuttings and volatilized to the atmosphere. Volatilization of MTBE occurred through both stems and leaves. The concentration of MTBE in the transpiration stream declined exponentially with height, indicating that the uptake and volatilization along the stems are an important removal mechanism of MTBE in phytoremediation. Volatilization, via diffusion from the stems, has not been directly measured previously. No volatile MTBE metabolites were detected; however, mass balance closure and metabolite detection were not primary objectives of this study. The greatest amount of MTBE in plant biomass was associated with the woody stems from the previous years growth, owing in part to the large biomass of stems. MTBE in the plant tissues appears to reach a steady state concentration and there does not appear to be an accumulation process that could lead to highly elevated concentrations relative to the groundwater source.

Phytoscreening for chlorinated solvents using rapid in vitro SPME sampling: Application to urban plume in Verl, Germany

Rapid detection and delineation of contaminants in urban settings is critically important in protecting human health. Cores from trees growing above a plume of contaminated groundwater in Verl, Germany, were collected in 1 day, with subsequent analysis and plume mapping completed over several days. Solid-phase microextraction (SPME) analysis was applied to detect tetrachloroethene (PCE) and trichloroethene (TCE) to below nanogram/liter levels in the transpiration stream of the trees. The tree core concentrations showed a clear areal correlation to the distribution of PCE and TCE in the groundwater. Concentrations in tree cores were lower than the underlying groundwater, as anticipated; however, the tree core water retained the PCE:TCE signature of the underlying groundwater in the urban, populated area. The PCE:TCE ratio can indicate areas of differing degradation activity. Therefore, the phytoscreening analysis was capable not only of mapping the spatial distribution of groundwater contamination but also of delineating zones of potentially differing contaminant sources and degradation. The simplicity of tree coring and the ability to collect a large number of samples in a day with minimal disruption or property damage in the urban setting demonstrates that phytoscreening can be a powerful tool for gaining reconnaissance-level information on groundwater contaminated by chlorinated solvents. The use of SPME decreases the detection level considerably and increases the sensitivity of phytoscreening as an assessment, monitoring, and phytoforensic tool. With rapid, inexpensive, and noninvasive methods of detecting and delineating contaminants underlying homes, as in this case, human health can be better protected through screening of broader areas and with far faster response times.

Fast separation and quantification method for nitroguanidine and 2,4-dinitroanisole by ultrafast liquid chromatography-tandem mass spectrometry.

Explosives are now persistent environmental pollutants that are targets of remediation and monitoring in a wide array of environmental media. Nitroguanidine (NG) and 2,4-dinitroanisole (DNAN) are two insensitive energetic compounds recently used as munitions explosives. To protect our environment and human health, the levels of these compounds in soils and waters need to be monitored. However, no sensitive analytical methods, such as liquid chromatography-tandem mass spectrometry (LC-MS/MS), have been developed for detecting these new compounds at trace levels and to be concurrently applied to monitor the common explosives. In general, the concentrations of explosives in either soil or water samples are very low and widely distributed. Therefore, a fast and sensitive method is required to monitor those compounds and increase our ability to find and address the threats they pose to human health and ecological receptors. In this study, a fast and sensitive analytical method has been developed to quantitatively determine NG and DNAN in soil, tap water, and river water by using ultrafast LC-MS/MS. To make this method a comprehensive analytical technique for other explosives as well, it has included other commonly used explosives in the method development, such as octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 1,3,5-trinitroper-hydro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), 2-amino-4,6-dinitrotoluene (ADNT), and pentaerythritol tetranitrate (PETN). The method detection limits (MDLs) of these compounds in soil ranged from 0.2 to 5 ppb, and a good linearity was obtained over a concentration range of 0.5-200 ppb. The recoveries of some compounds are equal to or better than the current EPA methods but with much higher sensitivities.

Time-weighted average SPME analysis for in planta determination of cVOCs.

The potential of phytoscreening for plume delineation at contaminated sites has promoted interest in innovative, sensitive contaminant sampling techniques. Solid-phase microextraction (SPME) methods have been developed, offering quick, undemanding, noninvasive sampling without the use of solvents. In this study, time-weighted average SPME (TWA-SPME) sampling was evaluated for in planta quantification of chlorinated solvents. TWA-SPME was found to have increased sensitivity over headspace and equilibrium SPME sampling. Using a variety of chlorinated solvents and a polydimethylsiloxane/carboxen (PDMS/CAR) SPME fiber, most compounds exhibited near linear or linear uptake over the sampling period. Smaller, less hydrophobic compounds exhibited more nonlinearity than larger, more hydrophobic molecules. Using a specifically designed in planta sampler, field sampling was conducted at a site contaminated with chlorinated solvents. Sampling with TWA-SPME produced instrument responses ranging from 5 to over 200 times higher than headspace tree core sampling. This work demonstrates that TWA-SPME can be used for in planta detection of a broad range of chlorinated solvents and methods can likely be applied to other volatile and semivolatile organic compounds.

Phytotechnologies – Preventing Exposures, Improving Public Health

Phytotechnologies have potential to reduce the amount or toxicity of deleterious chemicals and agents, and thereby, can reduce human exposures to hazardous substances. As such, phytotechnologies are tools for primary prevention in public health. Recent research demonstrates phytotechnologies can be uniquely tailored for effective exposure prevention in a variety of applications. In addition to exposure prevention, plants can be used as sensors to identify environmental contamination and potential exposures. In this paper, we have presented applications and research developments in a framework to illustrate how phytotechnologies can meet basic public health needs for access to clean water, air, and food. Because communities can often integrate plant-based technologies at minimal cost and with low infrastructure needs, the use of these technologies can be applied broadly to minimize potential contaminant exposure and improve environmental quality. These natural treatment systems also provide valuable ecosystem services to communities and society. In the future, integrating and coordinating phytotechnology activities with public health research will allow technology development focused on prevention of environmental exposures to toxic compounds. Hence, phytotechnologies may provide sustainable solutions to environmental exposure challenges, improving public health and potentially reducing the burden of disease.

PHYTOREMEDIATION OF BTEX HYDROCARBONS: POTENTIAL IMPACTS OF DIURNAL GROUNDWATER FLUCTUATION ON MICROBIAL DEGRADATION

Volatile hydrocarbons have multiple potential fates in phytoremediation. This research investigated the relationship between biodegradation and plant uptake of BTEX compounds in laboratory and field settings. At a phytoremediation site, preliminary studies revealed minimal uptake into trees and enhanced degradation potential in the rhizosphere and in the bulk soil. Increased oxygen transport to the vadose zone caused by diurnal rise and fall of the water table was hypothesized to enhance degradation in the bulk soil. A detailed greenhouse study was then conducted to investigate potential bioremediation impacts using field-site soil and DN34 hybrid poplar trees. In rhizosphere soils, the contaminated-planted reactor had significantly higher BTEX degrader populations versus the uncontaminated-planted reactor, as was anticipated. The bulk soil in the planted-contaminated reactor had increased degrader populations than the unplanted-contaminated soil or planted-uncontaminated soil, and planting increased degradation throughout the soil profile, not just in the limited volume of rhizosphere soils. Oxygen diffusive and advective transport into reactors was modeled and calculated. Oxygen input in planted reactors was at least 3 to 5 times higher than in unplanted reactors, and increasing oxygen input lead to increased degrader populations in a linear manner. These results combined with the knowledge that high-transpiration trees draw the contaminated groundwater to the capillary fringe and the rhizosphere indicate that phytoremediation can aid microbial degradation via multiple mechanisms: increasing degrader populations, increasing oxygen input via groundwater diurnal fluctuations, and transporting contaminants to the biologically-enriched soil profile.

Phytomonitoring of chlorinated ethenes in trees: a four-year study of seasonal chemodynamics in planta.

Long-term monitoring (LTM) of groundwater remedial projects is costly and time-consuming, particularly when using phytoremediation, a long-term remedial approach. The use of trees as sensors of groundwater contamination (i.e., phytoscreening) has been widely described, although the use of trees to provide long-term monitoring of such plumes (phytomonitoring) has been more limited due to unexplained variability of contaminant concentrations in trees. To assess this variability, we developed an in planta sampling method to obtain high-frequency measurements of chlorinated ethenes in oak (Quercus rubra) and baldcypress (Taxodium distichum) trees growing above a contaminated plume during a 4-year trial. The data set revealed that contaminant concentrations increased rapidly with transpiration in the spring and decreased in the fall, resulting in perchloroethene (PCE) and trichloroethene (TCE) sapwood concentrations an order of magnitude higher in late summer as compared to winter. Heartwood PCE and TCE concentrations were more buffered against seasonal effects. Rainfall events caused negligible dilution of contaminant concentrations in trees after precipitation events. Modeling evapotranspiration potential from meteorological data and comparing the modeled uptake and transport with the 4 years of high frequency data provides a foundation to advance the implementation of phytomonitoring and improved understanding of plant contaminant interactions.

Directional phytoscreening: contaminant gradients in trees for plume delineation.

Tree sampling methods have been used in phytoscreening applications to delineate contaminated soil and groundwater, augmenting traditional investigative methods that are time-consuming, resource-intensive, invasive, and costly. In the past decade, contaminant concentrations in tree tissues have been shown to reflect the extent and intensity of subsurface contamination. This paper investigates a new phytoscreening tool: directional tree coring, a concept originating from field data that indicated azimuthal concentrations in tree trunks reflected the concentration gradients in the groundwater around the tree. To experimentally test this hypothesis, large diameter trees were subjected to subsurface contaminant concentration gradients in a greenhouse study. These trees were then analyzed for azimuthal concentration gradients in aboveground tree tissues, revealing contaminant centroids located on the side of the tree nearest the most contaminated groundwater. Tree coring at three field sites revealed sufficiently steep contaminant gradients in trees reflected nearby groundwater contaminant gradients. In practice, trees possessing steep contaminant gradients are indicators of steep subsurface contaminant gradients, providing compass-like information about the contaminant gradient, pointing investigators toward higher concentration regions of the plume.