Micro-Spatial Variability of Soil Nitrate Following Nitrogen Fertilization and Drip Irrigation

Micro-spatial analysis of nitrate (NO₃), an environmental contaminant partially attributed to nitrogen fertilization, can be useful for estimating its distribution in soils. A study was conducted to determine the micro-spatial distribution of soil NO₃ using kriging and cokriging in a drip-irrigated and nitrogen-fertilized field. One hundred soil samples were collected in a regular grid pattern from a 10 m × 20 m plot, and analyzed for soil NO₃ and pH. The effect of reduced sample size on NO₃ estimation was also evaluated. The pH data indicated the soils were slightly acidic to neutral with log[NO₃] values ranging from 1.66 to 2.95. These parameters were inversely related; which was probably an attribute of soil nitrification process. Sample variograms and cross-variograms suggested that the spatial distribution of pH and log[NO₃] could be described by linear models in the area studied, as indicated by small MSE (mean sum error), and RKV (reduced kriging variance) values close to 1. Contour maps based on kriging and cokriging estimates indicated greater homogeneity of the variables in the south-north direction than the east-west, except for zones of high NO₃ and low pH in the north-central edge and north-east corner of the grid area. Cokriging of log[NO₃] estimation, using pH data, improved MSE, MSSE (mean sum square error), MKV (mean kriging variance), RKV, CEE (correlation between estimated data and error), CEM (correlation between estimated and measured data) by 46, 31, 30, 22, 96, and 98%, respectively, as compared to kriging. Lower cokriging variance for any estimated log[NO₃] value, as compared to the kriging analysis, indicated that cokriging provided more accurate estimates. With reduced sample observations (n) for NO₃ similar conclusions were obtained; and the estimation accuracy was maintained up to n >70. Cokriging analysis with reduced n also curtailed the analytical cost, and facilitated NO₃ estimation by means of pH, which was measured at a cheaper cost.     

BTEX Sorption by Montmorillonite Organo-Clays: TMPA,Adam, HDTMA

Organo-clay can be utilized for the containment of environmentalpollutants originating from waste sites or accidental spills. Abatch study was conducted using organo-clays produced from aWyoming montmorillonite (SWy) and three organic cations(trimethylphenylammonium (TMPA), trimethylammonium adamantane(Adam), and hexadecyltrimethylammonium (HDTMA)) to characterizeBTEX (benzene, toluene, ethylbenzene, o-, m-, p-xylene) sorption. Sorption data were fitted to two models,with Freundlich resulting in greater correlations of the datathan the Langmuir model (R ² at P ≤0.001-0.05). The Freundlich conditional index (n _f),which describes the experimental sorption characteristics,decreased curvilinearly with organic-cation molecular weights,thus suggesting organo-clays with smaller cations had greaterhydrocarbon retention. Sorption of BTEX followed the order ofTMPA > Adam > HDTMA organo-clays. A similar sequence in themagnitudes of log K _d and log K _omsupportedthis finding. Positive log K _om/K _ow valuesfor TMPA and Adam derivatives indicated there was a greaterretention of BTEX by these organo-clays than octanol. The orderof log K _om for SWy-HDTMA, although concentration-dependent, was analogous to the log K _ow order,indicating partitioning was the dominant sorption mechanism forthe HDTMA-clay. Isotherms for SWy-TMPA and SWy-Adam followed aconvex up pattern. In contract, a concave up curvature, notedfor SWy-HDTMA isotherms, was probably caused by a cosorptiveenhancement process resulting from an effective increase in organic matter content of the organo-clay due to furtherhydrocarbon sorption,in concurrence with a decrease inadsorbate activity coefficients. Values of binding affinityconstant, K _f, for SWy-TMPA were consistently higherthan SWy-Adam. The K _f values determined for totalBTEX sorption by TMPA and Adam derivatives were higher thanthose for the individual hydrocarbons. With SWy-HDTMA, the same order was observed for benzene and toluene; however, ethylbenzene and xylenes had greater K _f values thanthat for the BTEX mixture, possibly due to higher partitioningaffinity of the larger alkylbenzenes. With SWy-HDTM, thesequence of K _f values was: ethylbenzene > m-xylene > p-xylene > o-xylene > toluene >benzene. Trends for SWy-TMPA and SWy-Adam were in contrast tothat of the partitioning order, suggesting that adsorption, ratherthan partitioning, was the primary sorption mechanism for thesetwo organo-clays. With respect to the equilibriumconcentrations, the sorbed amounts for total BTEX mixture weregenerally higher than those for the individual compounds. Ascompared to benzene and toluene, the large-size alkylbenzenesshowed greater partitioning affinity due to their high hydrophobicity.