Elemental composition and moisture prediction in manure by portable X-ray fluorescence spectroscopy using random forest regression.

Manure elemental composition determination is essential to develop farm nutrient budgets and assess environmental risk. Portable X-ray fluorescence (PXRF) spectrometers could facilitate hazardous waste-free, rapid, and cost-effective elemental concentration determinations. However, sample moisture is a problem for elemental concentration determination by X-ray methods. The objective of this study was to quantify the effect of sample moisture content, predict moisture content, and correct for moisture effect on elemental concentration determinations in livestock manure. Oven-dried manure samples (n = 40) were ground and adjusted to five moisture ranges of (w/w moisture) <10%, 10-20%, 20-30%, 40-50%, and 60-70%. Samples were scanned by PXRF for 180 s using a vacuum (<1,333 Pa) and without a filter. The presence of moisture negatively affected elemental determination in manure samples. Calibrations (n = 200) were prepared using random forest regression with detector channel counts as independent variables. A three-step validation was performed using all the data, random cross-validation and external validation. The back end of the spectrum (14-15 keV) had strong predictive power (r2  = .98) for moisture content. The random forest approach increased r2 between PXRF and wet chemical methods from <.66 to >.90 for P, K, and Mg and from .78 to .98 for Fe, compared with linear, nonlinear, and Lucas-Tooth and Price equations. These results indicated that elemental concentration can accurately be measured in dried and moist manure samples using PXRF and expands the potential applications of PXRF to in situ elemental determinations for agricultural and environmental samples.

Assessment of dissolved organic carbon and iron effects on water color between a forest and pasture-dominated fine-scale catchment in a Central Appalachian region, West Virginia.

Dissolved organic carbon (DOC) and iron (Fe) have been observed to be the important contributors to surface water brownification. Additionally, the DOC quality influences water color by forming Fe-DOC complexes that provide additive effects and is influenced by dominant land use type within watersheds. However, the influence of quantity and quality of DOC on Fe and water color is poorly understood in headwater streams. The aim of this study was to investigate the effects of DOC and Fe on water color in forest (FC) and pasture (GFC) fine-scale watersheds to remove the confounding effects of climate and soil parent material. Significant differences of DOC, Fe, and water absorbance at 420 nm (a420) between FC and GFC were found (p < 0.05). A dominant contribution to water color was from DOC (95.5 - 63.7%) with a decreasing trend when Fe increased from 0.011 to 0.258 mg L-1. There were no significant interactions between FC and GFC and Fe on either a420/DOC (p = 0.06) or specific ultraviolet absorbance at 254 nm (SUVA254) (p = 0.30). Increasing values of a420/DOC and SUVA254 were significantly associated with increasing Fe concentration (p < 0.01). Significant interactions were found between FC and GFC and Fe on spectral slope ratio (S ratio) (p < 0.01). The response rate of S ratio with increasing Fe per unit was 0.235 for GFC while it was - 11.043 for FC. These differences indicate that land use may change the quality of DOC, influence Fe-DOC interactions, and thus affect water color. Linking the effects of soil Fe and DOC and headwater Fe and DOC may help identify optimal management practice to mitigate surface water brownification.

Uptake and speciation of zinc in edible plants grown in smelter contaminated soils.

Heavy metal accumulation in edible plants grown in contaminated soils poses a major environmental risk to humans and grazing animals. This study focused on the concentration and speciation of Zn in different edible plants grown in soils contaminated with smelter wastes (Spelter, WV, USA) containing high levels of the metals Zn, Cu, Pb, Cd. Their accumulation was examined in different parts (roots, stem, and leaves) of plants and as a function of growth stage (dry seed, sprouting seed, cotyledon, and leaves) in the root vegetables radish, the leafy vegetable spinach and the legume clover. Although the accumulation of metals varied significantly with plant species, the average metal concentrations were [Zn] > [Pb] > [Cu] > [Cd]. Metal uptake studies were complemented with bulk and micro X-ray absorption spectroscopy (XAS) at Zn K-edge and micro X-ray fluorescence (µXRF) measurements to evaluate the speciation and distribution of Zn in these plant species. Dynamic interplay between the histidine and malate complexation of Zn was observed in all plant species. XRF mapping of spinach leaves at micron spatial resolution demonstrated the accumulation of Zn in vacuoles and leaf tips. Radish root showed accumulation of Zn in root hairs, likely as ZnS nanoparticles. At locations of high Zn concentration in spinach leaves, µXANES suggests Zn complexation with histidine, as opposed to malate in the bulk leaf. These findings shed new light on the dynamic nature of Zn speciation in plants.

Portable X-Ray Fluorescence Spectroscopy for Rapid and Cost-Effective Determination of Elemental Composition of Ground Forage.

The recent development of portable X-ray fluorescence spectrometers (PXRF) has created new avenues for rapid plant elemental concentration determination at reduced cost while avoiding hazardous chemicals. A few studies have indicated the potential use of PXRF for homogenous plant tissue analysis. However, there is a lack of information for analysis of heterogeneous plant samples like livestock forage, which consists of a mixture of several species and plant parts, each varying in elemental concentration. Our objective was to evaluate PXRF for forage analysis, specifically the effect of forage particle size and scan time on important elements including P, K, Ca, and Fe determination. Hay samples (n = 42) were oven dried (60°C for 3 days) and ground into three particle sizes (≤0.5 mm, 0.25-0.5 mm and 1-2 mm). Prepared samples were scanned by PXRF using a vacuum (<10 torr) without a filter. Samples were placed in cups over thin prolene X-ray film and scanned for 180 s. A subset (n = 29) were also scanned for 60 and 120 s. PXRF counts for P, K, Ca, and Fe were compared with laboratory Inductively Coupled Plasma Optical Emission Spectroscopy (ICP) determinations, using regression models. Results indicated that these elements could potentially be determined with PXRF (r 2 ≥ 0.70) in heterogeneous forage samples. Relationship strength increased with decreasing particle size, however, the relationship was still strong (r 2 ≥ 0.57) at the largest particle size. Scanning time did not affect the relationship with ICP concentration for any of the particle sizes evaluated. This work demonstrated that with the right sample preparation PXRF can obtain results comparable to acid digestion and ICP regardless of sample composition, and suggests the potential for in situ determinations.

Heterogeneous selenite reduction by zero valent iron steel wool.

Mine drainage from the low-sulfur surface coal mines in southern West Virginia, USA, is circumneutral (pH > 6) but contains elevated selenium (Se) concentrations. Removal of selenite ions from aqueous solutions under anoxic condition at pH 6-8.5 by zero valent iron steel wool (ZVI-SW) was investigated in bench-scale kinetic experiments using wet chemical, microscopic and spectroscopic techniques (X-ray photoelectron spectroscopy). ZVI-SW could effectively and efficiently remove SeIV from solution with pH 6-8.5. A two-step removal mechanism was identified for SeIV reduction by ZVI-SW. The proposed mechanism was electrochemical reduction of SeIV by Fe0 in an initial lag stage, followed by a faster heterogeneous reduction, mediated by an FeII-bearing phase (hydroxide or green rust). Solution pH was a critical factor for the kinetic rate in the lag stage (0.33 h-1 for pH > 8 and 0.10 h-1 for pH 6-8). The length of lag stage was 20-30 min as determined by the time for dissolved FeII concentration to reach 0.30 ± 0.04 mg L-1 which was critical for induction of the faster stage. About 65% of the initial SeIV was reduced to Se0, the primary reductive product in both stages.

Denitrification kinetics in biomass- and biochar-amended soils of different landscape positions.

Knowledge of how biochar impacts soil denitrification kinetics as well as the mechanisms of interactions is essential in order to better predict the nitrous oxide (N2O) mitigation capacity of biochar additions. This study had multiple experiments in which the effect of three biochar materials produced from corn stover (Zea mays L.), ponderosa pine wood residue (Pinus ponderosa Douglas ex Lawson and C. Lawson), switchgrass (Panicum virgatum L.), and their corresponding biomass materials (corn stover, ponderosa pine wood residue, and switchgrass) on cumulative N2O emissions and total denitrification in soils from two different landscape positions (crest and footslope) were studied under varying water-filled pore space (40, 70, and 90% WFPS). Cumulative N2O emissions were reduced by 30 to 70% in both crest and footslope soils. The effect of biochars and biomass treatments on cumulative N2O emissions and total denitrification were only observed at ≥40% WFPS. The denitrification enzyme activity (DEA) kinetic parameters, K s (half-saturation constant), and V max (maximum DEA rate) were both significantly reduced by biochar treatments, with reductions of 70-80% in footslope soil and 80-90 % in the crest soil. The activation energy (E a) and enthalpy of activation of DEA (ΔH) were both increased with biochar application. The trends in DEA rate constants (K s and V max) were correlated by the trends of thermodynamic parameters (activation energy E a and enthalpy of activation ΔH) for denitrifying enzyme activity (DEA). The rate constant V max/K s evaluated the capacity of biochars to mitigate the denitrification process. Denitrifying enzyme kinetic parameters can be useful in evaluating the ability of biochars to mitigate N2O gas losses from soil.

Effect of alcohols on the retention mechanisms of Cd and Zn on Wyoming bentonite and illite.

The effects of ethanol- and methanol-water mixtures on Zn and Cd sorption onto bentonite and illite were investigated at low initial metal concentration (< or =10(-5) M) and low ionic strength (2.5 mM Ca(NO3)2). For all cosolvent fractions, the percent coverage of Zn and Cd to clay minerals was low (<5%) and independent of the solution dielectric constant, epsilon, except for Zn at 10 microM. Cadmium sorption to bentonite and illite was independent of epsilon. Zinc sorption varied significantly between clay types, cosolvent type, and cosolvent fraction. The partitioning of Zn to bentonite increased from 0 to 10% alcohol-water fraction and decreased after 10%. The same pattern was observed for the partitioning of Zn on illite in methanol-water mixtures. In ethanol-water mixtures, Kf for Zn on illite increased continuouslyfrom 0 to 50% ethanol. The decreased partitioning and hence mobility of Zn to bentonite and illite after 10% alcohol (only in methanol-water mixtures for illite) suggests a potential environmental threat resulting from increased transport of this metal in subsurface environments where these cosolvents are present.