William L. Kingery

Accumulation of heavy metals in a long-term poultry waste-amended soil

Various metals are added to poultry diets to facilitate weight increase and disease prevention. The large amounts of poultry waste produced annually are dispersed intensively over relatively small areas of land, resulting in accumulations that pose potential environmental risks to the surface and groundwater. The focus of this study was to assess the distribution of heavy metals among various solid-phase fractions in soil profiles from a 25-year poultry waste-amended soil. Copper and Zn accumulated close to the soil surface where the total amounts of Cu and Zn in waste-amended soils were significantly higher than in nonamended soils. The total metal concentrations in amended soils were not critically high. Copper in the amended soil was present mostly in the organic matter (OM) fraction (46.9%), whereas Zn was found in the easily reducible oxide (ERO) fraction (47.3%). This suggests that the Cu and Zn in this long-term amended soil are potentially bioavailable and mobile. We observed the mobility of Zn through much of the soil profile of the long-term waste-amended soil. Zinc in this soil profile was found primarily in forms of the residual (RES) and crystalline iron oxide bound (CryFe) fractions, followed by the organic matter-bound and exchangeable (EXC) fractions.

New approach to studies of heavy metal redistribution in soil

Abstract The bioavailability and mobility of heavy metals in soils is dependent upon redistribution processes between solution and solid phases and among solid-phase components. This paper reviews the definitions and applications of two newly developed parameters, the redistribution index and the reduced partitioning parameter, in quantifying redistribution processes of heavy metals in contaminated soils. The redistribution index depicts the removal/attainment of metal-contaminated soils from/to the fractional distribution pattern characteristic of non-amended soils, while the reduced partitioning parameter quantifies the relative binding intensity of heavy metals in soils. Over time, metal salt-spiked and sludge-amended soils approached the fractional distribution pattern of non-amended soils. The rates of redistribution of metals and their binding intensity in soils were affected by the metal species, loading levels and soil properties. Metals in contaminated soils at low loading levels approach the fractional distribution pattern of non-amended soil more rapidly than those at high loading levels. The sequence order of approach by metals to the fractional distribution pattern of non-amended soil was: Cd>Cu>Ni=Zn>Cr. In both non-amended and contaminated soils, Cr had the highest binding intensity, Cd the lowest, and Cu, Ni and Zn, intermediate values. In addition to our own data, primarily on metal salt-spiked soils, these two indices are also used to evaluate redistribution processes of heavy metals in sewage sludge-amended soils from other published reports.

Arsenic solubility and distribution in poultry waste and long-term amended soil.

The purpose of this study was to quantify the solubility and distribution of As among solid-phase components in poultry wastes and soils receiving long-term poultry waste applications. Arsenic in the water-soluble, NaOCl-extractable (organically bound), NH(2)OH x HCl-extractable (oxide bound) and residual fractions were quantified in an Upper Coastal Plain soil (Neshoba County, MS) that received annual waste applications. After 25 years, As in the amended soil had a mean of 8.4 mg kg(-1) compared to 2.68 mg kg(-1) for a non-amended soil. Arsenic in the amended soil was mainly in the residual fraction (72% of total), which is generally considered the least bioavailable fraction. Arsenic in poultry waste samples was primarily water-soluble (5.3-25.1 mg kg(-1)), representing 36-75% of the total As. To assess the extent of spatial heterogeneity, total As in a 0.5-ha area within the long-term waste-amended field was quantified. Soil surface samples were taken on 10-m grid points and results for total As appeared negatively skewed and approximated a bimodal distribution. Total As in the amended soil was strongly correlated with Fe oxides, clay and hydroxy interlayered vermiculite concentrations, and negatively correlated with Mehlich III-P, mica and quartz contents.

Online High-Performance Size Exclusion Chromatography−Nuclear Magnetic Resonance for the Characterization of Dissolved Organic Matter

The substantial heterogeneity of dissolved organic matter (DOM) inhibits detailed chromatographic analysis with conventional detectors as little structural information can be obtained in the presence of extensive coelution. Here we examine the direct hyphenation of high-performance size exclusion chromatography (HPSEC) with nuclear magnetic resonance (NMR) spectroscopy to determine how size-distinguished fractions differ in composition. The results support the applicability of using HPSEC to generate more homogeneous fractions of DOM prior to NMR analysis and demonstrate that structure is significantly altered with size. The largest fractions are enriched in carbohydrate- and aromatic-type structures. The midsized material is substantial and is representative of carboxyl-rich alicyclic molecules (CRAMs). The smallest material has strong signatures of material derived from linear terpenoids (MDLT). Both CRAMs and MDLT have been recently hypothesized as major components of DOM, and detection by HPSEC-NMR confirms their existence as unique and separable entities. This preliminary work focuses on NMR hyphenation to HPSEC due to widespread use of HPSEC to characterize DOM. Online hyphenation is useful not only for time-efficient analysis of DOM but also for that of other highly complex samples such as those found in many environmental analyses.

The application of multidimensional NMR to the study of soil humic substances.

Humic substances are the most abundant organic macromolecules in soils, and comprehension of their chemical structure is essential to understanding their role in terrestrial ecosystems. The one-dimensional nuclear magnetic resonance (NMR) spectroscopy techniques now used widely to study humic substances have provided important insight into humic structures, but the complexity of these macromolecules gives rise to resonance signals that are broad and have spectral overlap. This has prevented the definitive functional group assignments necessary for structural determination. Hence, interest has focused on more powerful two-dimensional NMR experiments, such as the homonuclear TOtal Correlation SpectroscopY (TOCSY) and Heteronuclear Multiple Quantum Coherence (HMQC), which were employed in the study of a soil humic acid standard. The purpose of this paper is to outline the potential of these techniques to the study of soil humic structures. The 2-D spectra produced were extremely encouraging, with multitudes of cross-peaks produced from both TOCSY and HMQC experiments. The identification of fatty ester/acid chains and amino acid couplings are given as examples. Results obtained with these NMR experiments indicate substantial improvements in functional group assignment capabilities and the potential for marked progress in the determination of the chemical structure of soil humic substances.

Hydrodynamic Modeling of St. Louis Bay Estuary and Watershed Using EFDC and HSPF

Abstract St. Louis Bay estuary is a vital water body in the Mississippi Gulf Coast Region and greatly affects the water quality in the Mississippi Sound. As the first step of total maximum daily load (TMDL) study, a hydrodynamics model was developed by integrating Hydrological Simulation Program Fortran (HSPF) and Environmental Fluid Dynamics Code (EFDC). In this application the EFDC model was configured to simulate time-varying surface water elevation, velocity, salinity, and water temperature. The HSPF was applied to compute the fresh water discharge from the upstream watersheds. The model reasonably simulated the tidal range and phase. The simulated water temperature and salinity showed good and fairly good agreement with observations. The calculated correlation coefficients between computed and observed velocity were lower compared with those for water level, temperature, and salinity, but the magnitudes of simulated velocity were found to be in the range of observed data. The wind data was found to have strong impacts on velocity simulation by modeling verification tests. Near the study area, there is wind data available only at one station, which has been applied to the entire modeling domain. The lack of high-resolution wind data makes it very difficult to simulate the velocity distribution well. It is anticipated and recommended that the development of this model be continued to synthesize additional field data into the modeling process.

Plinthite formation in the coastal plain region of Mississippi

Plinthite is a redoximorphic feature of many highly weathered soils and is considered to be an iron-rich and humus-poor pedogenic product that hardens irreversibly on exposure to sunlight. Soil conditions and the pedogenic processes responsible for plinthite formation are understood only within a general framework, lacking a minimum set of the conditions necessary and sufficient to predict which soils contain plinthite. Four plinthite-bearing pedons are described, classified, and analyzed to determine their physical, chemical, and mineralogical properties. In addition, detailed elemental analysis of the whole soil, clay fraction, plinthite nodules, and excised zones of Fe-accumulation and Fe-depletion was performed to estimate if Fe and Sc may be depleted or accumulated preferentially in these fractions. Iron, preferentially associated with the clay fraction, accumulated in the illuvial horizons as a result of the clay eluviation-illuviation processes. Iron is also preferentially incorporated into zones of Fe-accumulation, including plinthite nodules; however, Sc does not segregate between zones of Fe-accumulation and Fe-depletion. The concentration divergence of Fe and Sc suggests that plinthite is primarily an oxidation-reduction process involving diffusion processes. Plinthite formation occurs in conjunction with Btx horizon degradation and in a zone of Fe-accumulation having a firm to very firm consistency.

Applications of NMR Spectroscopy for Studies of the Molecular Compositions of Humic Substances

Abstract Considerable effort has focused in recent years on applications of cross polarization magic angle spinning (CPMAS) 13C nuclear magnetic resonance (NMR) spectroscopy to studies of the compositions of humic substances (HS). This technique has provided valuable information on some functionalities, and about the relative abundances of these in the macromolecules. The spectra provide an excellent ‘fingerprint’ technique for comparing fractions from the same source, and similar fractions from different sources. However, in its present state of development, CPMAS 13C NMR spectroscopy cannot provide detailed structural information about the heterogeneous mixture of components that compose HS. The development of powerful NMR spectrometers has caused interest to focus on applications of proton (1H) NMR spectroscopy to studies of humic structures. The present contribution highlights the uses of 1H NMR and combinations of 1H and 13C NMR for studies of aspects of the compositions of humic fractions. A fulvic acid isolated at pH 12.6 from the humified portions of a moss culture growing on a rock surface was studied using one dimensional (1-D) 1H NMR, 2-D 1H-1H COorrelation SpectroscopY (COSY), 2-D 1H-1H TOtal Correlation SpectroscopY (TOCSY), and 2-D 1H-13C Heteronuclear Multiple Quantum Coherence (HMQC) spectroscopy using high field 500 MHz and 600 MHz spectrometers. The spectra illustrate the potential of the techniques for determinations of structures. However, it will be necessary to develop improved fractionation procedures in order to be able to obtain an advanced awareness of the structures in the more highly humified HS.

Fecal coliform modeling under two flow scenarios in St. Louis Bay of Mississippi

St. Louis Bay, along with its two major tributaries, Wolf River and Jourdan River, are included in the Mississippi 1998 Section 303(d) List for violation of the designated water use of recreation and shellfish harvesting. Fecal coliform was identified as one of the pollutants that caused the water quality impairment. In order to facilitate the total maximum daily loads (TMDL) development, the fecal coliform dynamics was investigated under 2 flow scenarios with a calibrated and validated modeling framework by integration of Environmental Fluid Dynamic Code (EFDC) and Hydrological Simulation Program Fortran (HSPF). EFDC was used to model the hydrodymics and fecal coliform transportation in the Bay and the tributaries, whereas HSPF was applied to compute the flow and fecal coliform loadings from the watersheds. The total amount of precipitation in the dry year simulation corresponds to a 50-year return period of low flow condition, and a 10-year return period of high flow condition for wet weather simulation. For EFDC modeling, the fecal coliform sources considered were the contributions from the 2 upper watersheds (no tidal influence), the 28 small surrounding watershed, and 12 municipal, industrial, and domestic point sources. When simulating the fecal coliform loadings from the 2 upper watersheds using HSPF, the simulated non-point source loadings of fecal coliform included wildlife, land application of hog and cattle manure, land application of poultry litter, and grazing animals. The EFDC modeling results indicated that the wet weather exerted greater stress on fecal coliform water quality conditions. The number of exceedance of fecal coliform water quality standard in wet year simulation is much higher than that in dry year simulation. The impact of the upper rural watersheds loads on fecal coliform levels in the St. Louis Bay is much less significant than that from the surrounding urban runoff. Fecal coliform TMDL development should be based on high flow conditions since the decision makers are more concerned about worse scenarios. This fecal coliform modeling research would provide useful information of critical condition selection for TMDLs development in similar coastal areas.

Effect of tillage on microbial characteristics and herbicide degradation in a Sharkey clay soil.

Abstract Field and laboratory studies were conducted at Stoneville, MS, from 1996 to 1998 to determine the influence of subsoiling (SS) and conventional tillage (CT) of a Sharkey clay soil on microbial characteristics and herbicide degradation. Soil samples obtained from imazaquin-treated and nontreated plots from the soybean row and interrow position were analyzed. Because only the row position is actually disturbed by SS, a comparison of row and interrow position on the parameter was conducted. Imazaquin (preemergence, 140 g ai ha−1) had no effect on microbial populations, microbial enzyme activity (fluorescein diacetate [FDA] hydrolysis and triphenyl-tetrazolium chloride [TTC] dehydrogenase), and organic carbon content. Estimates of microbial activity based on FDA hydrolysis and TTC dehydrogenase activity indicated greater activity under CT; however, microbial biomass and organic carbon were not affected by tillage or row position. A laboratory study assessed the degradation of carboxyl- and ring-labeled 2,4-D as influenced by tillage and row position. Soils from CT plots had an initially higher mineralization rate of 14C carboxyl-labeled 2,4-D compared to soils from SS plots; however, no effect of tillage or row position was observed on the cumulative amount of 14CO2 evolved 14 d after treatment (DAT) in 1996 and 18 DAT in 1998. In studies with ring-labeled 2,4-D, a higher 14CO2 evolution was detected in soils obtained from SS plots, regardless of row position, whereas a greater amount of radioactivity was observed in the unextractable fraction from CT soils. Because differences in 2,4-D mineralization between tillage regimes were minimal, adoption of SS as a tillage practice for heavy clay soils in the Mississippi Delta may have a limited effect on microbial characteristics and biodegradation of soil-applied herbicides. Nomenclature: 2,4-D; 2,4-DCP, 2,4-dichlorophenol; imazaquin; FDA, fluorescein diacetate; TTC, triphenyl-tetrazolium chloride; soybean, Glycine max (L.) Merr.