A Method to Preserve Wetland Roots and Rhizospheres for Elemental Imaging

Roots extensively interact with their soil environment but visualizing such interactions between roots and the surrounding rhizosphere is challenging. The ...

University of Delaware

Human exposure to volatile organic compounds (VOCs) via vapor intrusion (VI) is an emerging public health concern with notable detrimental impacts on public health. Phytoforensics, plant sampling to semi-quantitatively delineate subsurface contamination, provides a potential non-invasive screening approach to detect VI potential, and plant sampling is effective and also time- and cost-efficient. Existing VI assessment methods are time- and resource-intensive, invasive, and require access into residential and commercial buildings to drill holes through basement slabs to install sampling ports or require substantial equipment to install groundwater or soil vapor sampling outside the home. Tree-core samples collected in 2 days at the PCE Southeast Contamination Site in York, Nebraska were analyzed for tetrachloroethene (PCE) and results demonstrated positive correlations with groundwater, soil, soil-gas, sub-slab, and indoor-air samples collected over a 2-year period. Because tree-core samples were not collocated with other samples, interpolated surfaces of PCE concentrations were estimated so that comparisons could be made between pairs of data. Results indicate moderate to high correlation with average indoor-air and sub-slab PCE concentrations over long periods of time (months to years) to an interpolated tree-core PCE concentration surface, with Spearman's correlation coefficients (ρ) ranging from 0.31 to 0.53 that are comparable to the pairwise correlation between sub-slab and indoor-air PCE concentrations (ρ = 0.55, n = 89). Strong correlations between soil-gas, sub-slab, and indoor-air PCE concentrations and an interpolated tree-core PCE concentration surface indicate that trees are valid indicators of potential VI and human exposure to subsurface environment pollutants. The rapid and non-invasive nature of tree sampling are notable advantages: even with less than 60 trees in the vicinity of the source area, roughly 12 hours of tree-core sampling with minimal equipment at the PCE Southeast Contamination Site was sufficient to delineate vapor intrusion potential in the study area and offered comparable delineation to traditional sub-slab sampling performed at 140 properties over a period of approximately 2 years.

Phytoforensics: Trees as bioindicators of potential indoor exposure via vapor intrusion.

Phytoremediation is a sustainable remedial approach, although performance efficacy is rarely reported. In this study, we assessed a phytoremediation plot treating benzene, toluene, and chlorobenzene. A comparison of the calculated phytoremediation removal rate with estimates of onsite contaminant mass was used to forecast cleanup periods. The investigation demonstrated that substantial microbial degradation was occurring in the subsurface. Estimates of transpiration indicated that the trees planted were removing approximately 240,000 L of water per year. This large quantity of water removal implies substantial removal of contaminant due to large amounts of contaminants in the groundwater; however, these contaminants extensively sorb to the soil, resulting in large quantities of contaminant mass in the subsurface. The total estimate of subsurface contaminant mass was also complicated by the presence of non-aqueous phase liquids (NAPL), additional contaminant masses that were difficult to quantify. These uncertainties of initial contaminant mass at the site result in large uncertainty in the cleanup period, although mean estimates are on the order of decades. Collectively, the model indicates contaminant removal rates on the order of 10-10 kg/tree/year. The benefit of the phytoremediation system is relatively sustainable cleanup over the long periods necessary due to the presence of NAPL.

Phytoremediation removal rates of benzene, toluene, and chlorobenzene.

Increasing plant-availability of Si through soil amendment of Si-rich rice residues can decrease inorganic As without affecting Cd levels in grain under flooded soil conditions. However, the impacts of Si amendments on Cd and As uptake by rice under different flooding extents have not been reported. We investigated the effects of different flooding extent on As and Cd uptake by rice and accumulation in grain in well-weathered soil amended with Si-rich rice husk (Husk) or mixed charred/ashed rice husk (Ash). Our results show that Husk and to a lesser extent Ash amendments decreased grain As under both flooded (~40% and 20% decrease, respectively) and nonflooded (~75% decrease) conditions due to increased Si. Under flooded conditions grain As and yield is higher, and Husk amendment additionally decreased grain inorganic As by ~45%. Under nonflooded conditions grain Cd is higher and yield is lower, and Ash amendment decreased grain, husk, and straw Cd by ~40-50% not due to Si, but due to increased aboveground biomass and an increase in soil pH, which helped to retain Cd in soil. These data illustrate that rice residue addition to paddy soil can lower human health risk under both flooded and nonflooded conditions without affecting grain Zn and Fe.

Combined impacts of Si-rich rice residues and flooding extent on grain As and Cd in rice.

Emerging and fugitive contaminants (EFCs) released to our biosphere have caused a legacy and continuing threat to human and ecological health, contaminating air, water, and soil. Polluted media are closely linked to food security through plants, especially agricultural crops. However, measuring EFCs in plant tissues remains difficult, and high-throughput screening is a greater challenge. A novel rapid freeze-thaw/centrifugation extraction followed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis was developed for high-throughput quantification of 11 EFCs with diverse chemical properties, including estriol, codeine, oxazepam, 2,4-dinitrotoluene, 1,3,5-trinitroperhydro-1,3,5-triazine, bisphenol A, triclosan, caffeine, carbamazepine, lincomycin, and DEET, in three representative crops, corn, tomato, and wheat. The internal aqueous solution, i.e., sap, is liberated via a freeze/thaw cycle, and separated from macromolecules utilizing molecular weight cutoff membrane centrifugal filtration. Detection limits ranged from 0.01 μg L to 2.0 μg L. Recoveries of spiked analytes in three species ranged from 83.7% to 109%. Developed methods can rapidly screen EFCs in agriculture crops and can assess pollutant distribution at contaminated sites and gain insight on EFCs transport in plants to assess transmembrane migration in vascular organisms. The findings contribute significantly to environmental research, food security, and human health, as it assesses the first step of potential entry into the food chain, that being transmembrane migration and plant uptake, the primary barrier between polluted waters or soils and our food.

Green Analysis: High Throughput Analysis of Emerging Pollutants in Plant Sap by Freeze-Thaw-Centrifugal Membrane Filtration Sample Preparation-HPLC-MS/MS Analysis.

Uptake of seven organic contaminants including bisphenol A, estriol, 2,4-dinitrotoluene, N,N-diethyl-meta-toluamide (DEET), carbamazepine, acetaminophen, and lincomycin by tomato (Solanum lycopersicum L.), corn (Zea mays L.), and wheat (Triticum aestivum L.) was measured. The plants were grown in a growth chamber under recommended conditions and dosed by these chemicals for 19 days. The plant samples (stem transpiration stream) and solution in the exposure media were taken to measure transpiration stream concentration factor (TSCF). The plant samples were analyzed by a freeze-thaw centrifugation technique followed by high performance liquid chromatography-tandem mass spectrometry detection. Measured average TSCF values were used to test a neural network (NN) model previously developed for predicting plant uptake based on physicochemical properties. The results indicated that moderately hydrophobic compounds including carbamazepine and lincomycin have average TSCF values of 0.43 and 0.79, respectively. The average uptake of DEET, estriol, acetaminophen, and bisphenol A was also measured as 0.34, 0.29, 0.22, and 0.1, respectively. The 2,4-dinitrotoluene was not detected in the stem transpiration stream and it was shown to degrade in the root zone. Based on these results together with plant physiology measurements, we concluded that physicochemical properties of the chemicals did predict uptake, however, the role of other factors should be considered in the prediction of TSCF. While NN model could predict TSCF based on physicochemical properties with acceptable accuracies (mean squared error less than 0.25), the results for 2,4-dinitrotoluene and other compounds confirm the needs for considering other parameters related to both chemicals (stability) and plant species (role of lipids, lignin, and cellulose).

Investigating plant uptake of organic contaminants through transpiration stream concentration factor and neural network models.

The roots of aquatic plants, including rice, release oxygen into the subsurface, precipitating reduced metals, such as iron (Fe) and manganese (Mn), as plaques that form on the surface of the roots. These plaques are a unique habitat for microorganisms and a hotspot for biogeochemical cycling, including the toxic trace metalloid arsenic (As). However, studying plaque deposition and mineral composition in this spatially and temporally heterogeneous environment is challenging, particularly . Here, we describe a new technique for nondestructive and repeated rhizosphere sampling. We placed vinyl films that adhere Fe deposits from roots growing adjacent to the films into soil. The films were removed and replaced throughout plant growth and were characterized using a variety of spectroscopic (XRF imaging and Fe EXAFS) and microscopic (SEM and confocal) techniques. Fe deposits were most concentrated at lateral junctions and heterogeneity was apparent in the location and speciation of Fe-associated As in both pot and field studies. XRF imaging at multiple incident beam energies revealed that this As was mostly arsenate, although arsenite was present on the edge of the Fe deposit. Iron deposits were typically micron sized and consisted mostly of ferrihydrite, consistent with the data reported using conventional techniques. Moreover, Fe deposits were occupied by a variety of microorganisms. These films are a suitable technique to study a range of spatial and temporal questions regarding the biogeochemistry of aquatic plant roots.

A New Method to Capture the Spatial and Temporal Heterogeneity of Aquatic Plant Iron Root Plaque .

Arsenic (As) and cadmium (Cd) are two toxins that affect rice, and their ability to do so may be lessened by soil incorporation of rice husk residues. Rice husks are typically removed from fields and used as a fuel source at rice mills but contain silicon (Si) and other nutrients. It has previously been shown that soil incorporation of rice husk or charred husk can release Si to soil solution to decrease As uptake and promote As methylation, and studies suggest char can additionally decrease Cd availability through several potential mechanisms including adsorption, precipitation, liming, and growth dilution. Charring conditions will impact husk Si dissolution rate and potential to immobilize Cd and possibly methylated As. Here, we compared uncharred husk to husk biochars pyrolyzed at 450, 600, 750, and 900 °C for differences in Si dissolution rate and adsorption of Cd and dimethylarsinic acid (DMA)-the dominant methylated As species present in paddy soils and grain. We hypothesized that Si dissolution rate and Cd adsorption would decrease, and DMA adsorption would increase with pyrolysis temperature. Si release decreased with pyrolysis temperature in the general order: uncharred husk > 450 °C > 600 °C = 750 °C = 950 °C but those differences were not due to SiO crystallization with increasing temperature. Additionally, short (< 5 d) lab-based extractions underestimate Si release from uncharred husk while overestimating release from biochars. Controlling for pH changes/liming effect, adsorption isotherms showed very weak DMA adsorption, while Cd adsorption was favored on higher temperature (950 °C) biochar and was not predicted well by cation exchange capacity (CEC). When applied in a soil incubation study using non-contaminated soil, the biochar had no impact on Cd porewater concentrations while low temperature (450 °C) rice husk biochar led to the highest Si:As ratio. Biochar did not strongly influence Cd and DMA solubility at 1% w/w amendment.

Matt A. Limmer

Department of Plant and Soil Sciences

University of Delaware

A Method to Preserve Wetland Roots and Rhizospheres for Elemental Imaging

Matt A. Limmer

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Plant and Soil Sciences

University of Delaware

A Method to Preserve Wetland Roots and Rhizospheres for Elemental Imaging

Department of Plant and Soil Sciences