Using nonequilibrium thin-disc and batch equilibrium techniques to evaluate herbicide sorption

Nonequilibrium disc-flow techniques may better reproduce dynamic soil-pesticide interactions than traditional batch sorption studies. Batch kinetic and equilibrium experiments and dual-label thin-disc flow experiments were conducted with atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazine-2,4-diamine) and imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] using a Demopolis silt loam (loamy-skeletal, carbonatic, thermic, shallow Typic Udorthent; 8% clay, 62 g kg(-1) organic matter, 7.6 pH). Batch kinetic studies with both herbicides revealed an almost instantaneous rapid phase and a much slower gradual phase. The rapid phase was complete after 5 min and equilibrium was reached at 24 h. The rapid phase accounted for 74% and 12 to 30% of the total amounts adsorbed for atrazine and imazaquin, respectively. The sorption of both the rapid and 24-h isotherms for each herbicide best fit the Freundlich equation. The rapid and 24-h K(f) values of atrazine were 1.38 and 2.41, respectively, and the N value of both phases was approximately 0.93. For imazaquin, the rapid and 24-h K(f) values were 0.056 and 035, respectively, and the N value for the rapid phase of imazaquin was 0.71, compared with 0.86 for the 24-h isotherm. In the dual-label thin-disc flow experiments, the average partition coefficient for atrazine at the peak soil concentration point was 1.54. This value closely agreed with the observed rapid-phase K(f) value of 1.38. In contrast, the thin-disc flow experiments failed to detect any imazaquin retention. The thin-disc flow method can allow for a greater resolution of rapid sorption kinetics, which is impractical with batch studies. Along with dynamic partitioning data, the thin-disc flow method may provide kinetics data that may better complement environmental models than coefficients generated with batch techniques.     

Incubation time effects on imazaquin desorption as determined by nonequilibrium thin-soil disc flow

Because organic sorption in soil may never reach equilibrium, a thin-disc flow nonequilibrium method may be helpful in understanding herbicide-soil interactions. This research was conducted to (i) determine the influence of incubation time on imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] desorption from soil, (ii) examine the influence of solution flow velocities on desorption, and (iii) elucidate the most appropriate kinetic model to describe imazaquin leaching. Soil at 7.5% moisture w/w was treated with imazaquin and incubated for 24, 72, and 168 h. Treated soil was sealed in an in-line filter apparatus and rinsed with 5.0 mM CaCl2 at 0.33, 0.67, or 1.0 mL min(-1). Effluent was collected as 1.0-mL fractions for a total of 50 mL. Flow was stopped for 24 h. When flow resumed, fractions were collected for an additional 15 mL. After the initial desorption, 79% of the imazaquin incubated for 24 h was leached. Increasing incubation time beyond 24 h reduced imazaquin leaching. After both desorption events, 13% of the initially applied imazaquin remained in the soil incubated for 168 h, compared with 7% with soil incubated for 24 h. Elovich and Freundlich kinetics accounted for 98% of the variance observed in the imazaquin desorption curves. First-order and diffusion kinetics accounted for 91% of the variance. Incubating soil for 72 h before desorption reduced the rate of imazaquin desorption by approximately 12%, compared with the 24-h incubation treatment. Imazaquin desorption was not affected by wash solution flow rate. These data suggest that the kinetics of desorption in prolonged desorption events are limited by transport phenomena (i.e., particle and film diffusion).     

A spatial model approach for assessing windbreak growth and carbon stocks

Agroforestry, the deliberate integration of trees into agricultural operations, sequesters carbon (C) while providing valuable services on agricultural lands. However, methods to quantify present and projected C stocks in these open-grown woody systems are limited. As an initial step to address C accounting in agroforestry systems, a spatial Markov random field model for predicting the natural logarithm (log) of the mean aboveground volume of green ash ( Marsh.) within a shelterbelt, referred to as the log of aboveground volume, was developed using data from an earlier study and web-available soil and climate information. Windbreak characteristics, site, and climate variables were used to model the large-scale trend of the log of aboveground volume. The residuals from this initial model were correlated among sites up to 24 km from a point of interest. Therefore, a spatial dependence parameter was used to incorporate information from sites within 24 km into the prediction of the log of the aboveground volume. Age is an important windbreak characteristic in the model. Thus, the log of aboveground volume can be predicted for a given windbreak age and for values of other explanatory variables associated with a site of interest. Such predictions can be exponentiated to obtain predictions of aboveground volume for windbreaks without repeated inventory. With the capability of quantifying uncertainty, the model has the potential for large regional planning efforts and C stock assessments for many deciduous tree species used in windbreaks and riparian buffers once it is calibrated.     

Case Study: Chemical Screening at Eastman Kodak Company

This case study is the final installment in a four‐part series profiling environmental decision making at leading companies. © 2001 John Wiley & Sons, Inc.     

A general bioeconomic simulation model for annual-crop marine fisheries

A generalized bioeconomic simulation model of annual-crop marine fisheries is described and its use in marine fisheries management is demonstrated. The biological submodel represents the recruitment of new organisms into the fishery, the movement of organisms from one fishing area to another and from one depth to another, the growth of organisms and the mortality of organisms resulting both from natural causes and from fishing. The economic submodel represents the fishing effort exerted on each resource species, the monetary costs of fishing, the value of the harvest and the rent (or excess profits) to the fishery.Basic dynamics of the model results from changes in the number of organisms in the fishery over time, which can be summarized as a set of difference equations of the general form ΔN/Δt = R + I ? E ? M ? F where ΔN/Δt is the net change in number of organisms in the fishery over time, R is recruitment, I is immigration, E is emigration, M is natural mortality and F is fishing mortality. R is a driving variable, whereas I, E, M and F are functions of the state of the system at any given point in time. The model can be run in a deterministic or stochastic mode. Values for parameters affecting rates of recruitment, movement, growth, natural mortality and fishing mortality can be selected from uniform, triangular or normal distributions.Use of the model within a fisheries-management framework is demonstrated by evaluating several management alternatives for the pink shrimp (Penaeus duorarum) fishery on the Tortugas grounds in the Gulf of Mexico. Steps involved in use of the model, including parameterization, validation, sensitivity analysis and stochastic simulations of management policies, are explained.     

A flume study of drift in marine infaunal amphipods (Haustoriidae)

Amphipods of the infaunal family Haustoriidae are characteristic of high-energy marine sands and occur both in the sediment and the overlying water column. Sediments in this habitat are subject to constant reworking by tidal currents, suggesting that resident amphipod populations are affected by this disturbance in a phenomenon similar to freshwater invertebrate drift. A controlled-velocity laboratory flume was used to examine the effect of haustoriid density, current velocity, illumination, and food availability on drift rates to determine a causal basis for drift. Drift is densityindependent and greatest at night and during high current flow; it is also greater at night from sterile sediment than from untreated sand. Flume transport was usually less than 10% of amphipods present in the sediment. Haustoriids captured downstream were mostly adults occurring in a 1:1 sex ratio, suggesting no obvious function of drift in reproduction. Current-induced displacement of haustoriids may produce the patchiness in distribution observed in nature. Disturbance of the bed could also function to keep amphipod densities below the carrying capacity of the local environment. In certain cases, food limitation may cause amphipods to actively leave the substrate. Under all conditions, greater drift rates in darkness are probably adaptive in avoidance of predators. Despite the nature of sediment movement in a high-energy environment, haustoriid drift may have an active as well as passive component.     

Localized defecation by pike: a response to labelling by cyprinid alarm pheromone?

Fathead minnows (Pimephales promelas) that have never encountered a predatory pike (Esox lucius), are able to detect conspecific alarm pheromone in a pike's diet if the pike has recently consumed minnows. It remains unclear how this minnow alarm pheromone is secreted by pike and if a pike is able to avoid being labelled as a potential predator by localizing these cues away from its foraging range. The first experiment determined that minnow alarm pheromone is present in pike feces when pike are fed minnows. Individual fathead minnows exhibited a fright response to a stimulus of pike feces if the pike had been fed minnows, but not if the pike had been fed swordtails, which lack alarm pheromone. Individual minnows also exhibited a fright reaction to alarm pheromone in the water (which contained no feces) housing pike which had been fed minnows, suggesting that alarm pheromone is also released in urine, mucous secretions and/or via respiration. The second experiment determined that test pike spent a significantly greater proportion of time in the home area of the test tanks (i.e. where they were fed) but the majority of feces were deposited in the opposite end of the test tank. By localizing their defecation away from the home or foraging area, pike may be able to counter the effects of being labelled as a predator by the alarm pheromone of the prey species.     

High-energy milling to decontaminate soils polluted by polychlorobiphenyls and atrazine

Mechanical energy has been used so far for running chemical reactions and for preparing new materials in absence of solvents. Very recently, the technology has been applied to solve environmental problems. In this paper, we describe the application of high-energy milling (HEM) for the remediation of soils contaminated by chlorinated organic compounds such as polychlorobiphenyls (PCBs) and agrochemicals like atrazine. NaBH₄ and LiAlH₄ have been successfully used for the total dehydrohalogenation of both classes of compounds, leaving a residue lower than 2 ppmw of the starting compound in the treated soil. LiAlH₄ was found to be more active than NaBH₄.     

Partitioning gas tracer tests for measurement of water in municipal solid waste

A key component in the operation of almost all bioreactor landfills is the addition of water to maintain optimal moisture conditions. To determine how much water is needed and where to add it, in situ methods are required to measure water within solid waste. Existing technologies often result in measurements of unknown accuracy, because of the variability of solid waste materials and time-dependent changes in packing density, both of which influence most measurement methods. To overcome these problems, a new technology recently developed by hydrologists for measuring water in the vadose zone--the partitioning gas tracer test--was tested. In this technology, the transport behavior of two gas tracers within solid waste is used to measure the fraction of the void space filled with water. One tracer is conservative and does not react with solids or liquids, while a second tracer partitions into the water and is separated from the conservative tracer during transport. This technology was tested in four different solid waste packings and was capable of determining the volumetric water content to within 48% of actual values, with most measurement errors less than 15%. This technology and the factors that affect its applicability to landfills are discussed in this paper.