Large‐Scale Fine‐Resolution Hydrological Modeling Using Parameter Regionalization in the Missouri River Basin

This study simulated crop and water yields in the Missouri River Basin (MRB; 1,371,000 km²), one of the largest river basins in the United States, using the Soil and Water Assessment Tool (SWAT) at a fine resolution of 12‐digit Hydrological Unit Codes (HUCs) using the regionalization calibration approach. Very few studies have simulated the entire MRB, and those that have developed were at a coarser resolution of 8‐digit HUCs and were minimally calibrated. The MRB was first divided into three subbasins and was further divided into eleven regions. A “head watershed” was selected in each region and was calibrated for crop and water yields. The parameters from the calibrated head watershed were extrapolated to other subwatersheds in the region to complete comprehensive spatial calibration. The simulated crop yields at the head watersheds were in close agreement with observed crop yields. Spatial validation of the aggregated crop yields resulted in reasonable predictions for all crops except dryland corn in a few regions. Simulated and observed water yields in head watersheds and also in the validation locations were in close agreement in naturalized streams and poor agreement in streams with high groundwater‐surface water interactions and/or reservoirs found upstream of the gauges. Overall, the SWAT model was able to reasonably capture the hydrological and crop growth dynamics occurring in the basin despite some limitations.     

A method for the analysis of organophosphorus pesticide residues in Mexican axolotl

A method based on matrix solid-phase dispersion (MSPD) was developed for quantitative extraction of three organophosphorus pesticides (OPPs) from the Mexican axolotl, Ambystoma mexicanum. The determination was carried out using high- performance liquid chromatography (HPLC) with diode array spectrophotometric UV detection (DAD). The MSPD extraction with octadecylsilyl (C18) sorbent combined with a silica gel clean-up and acetonitrile elution was optimised for chlorpyrifos, fenthion and methyl parathion. The method was validated, yielding recovery values higher than 90%. The precision, expressed as the relative standard deviation (RSD), was less than or equal to 6% in muscle samples at spiking levels of 10 and 5 ppm. Linearity was studied from 15 to 60 ppm for chlorpyrifos and fenthion, and from 7.5 to 30 ppm for methyl parathion. The limits of detection (LODs) were found to be less than or equal to 0.5 ppm_.This method was applied to the analysis of samples from a chlorpyrifos-exposed axolotl, demonstrating its use as an analytical tool for toxicological studies.     

Simple analytical method for determination of pesticide residues in human serum by liquid chromatography tandem mass spectrometry

The aim of this study was to develop an analytical method for the determination of residues of organophosphorus and carbamate pesticides which are widely used in Tunisia. This method involves a liquid-liquid extraction procedure followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for the identification and quantification of compounds. Ionization of molecules was performed by the electrospray mode. Multiple reactions monitoring (MRM) was the acquisition mode used for the monitoring of two MS/MS transitions for each compound. The average recoveries obtained, at three different fortification levels, ranged between 65% and 106% for most of the pesticides studied, except for methamidophos (lower than 25%).The linearity of the method was in the range of 5 to 50 μ g/L with a correlation coefficient from 0.995 to 0.999, depending on the analyte. The estimated limit of detection and limit of quantification were 2 μ g/L and 5 μ g/L, respectively. The precision of the analytical procedure was satisfactory and the coefficients of variation, evaluated at three concentration levels were lower than 15% for most pesticides studied. The application of the method was investigated in a population of agricultural workers chronically exposed to various pesticides some of which, such as carbofuran, carbendazim, methomyl and pirimicarb, were detected in some serum samples.     

Numerical simulation of evaporation of volatile liquids

The paper presents the results of the validation of the developed pool evaporation model using literature and our own experimental data. The proposed model was used to examine the effect of wind velocity and pool sizes on the evaporation rate of volatile liquid (hexane). Contrary to the semi-empirical evaporation model widely used in hazard assessment, stronger dependence of evaporation rate on pool size at low wind speeds is obtained.     

Validation of Urban Emission Inventories

Two emission validation methods are presented. The first method focuses on the precision of the emission factors and the accuracy of modelled traffic flows. Emission factors derived from the COPERT II methodology are compared with on-board emission measurements and modelled traffic flow rates are compared with observations. The second validation method focuses on the completeness of the inventory, i.e. coverage of all sources. The method compares measured pollutant fluxes in the urban plume with the downwind transported and dispersed emissions integrated over plume width and mixing height. Both methods seem to indicate that traffic emission factors used in the urban emission inventories show large uncertainties. Besides the lack of measurement precision this is mainly induced by external influence factors like driving behaviour and vehicle maintenance.     

Modelling feeding flow related shrinkage defects in aluminum castings

The process modelling of shape casting is geometrically complex and computationally very challenging. Besides the three-dimensional complex shapes with multiple domains, the defects of interest to industry arise as a consequence of the interaction amongst a range of phenomena. Conventionally, the key phenomena and defect prediction are modelled through empirical relations applied to the simulation results. Such approaches are neither comprehensive nor reliable. This paper presents a 3-D model that is capable of predicting the formation of shrinkage defects explicitly as a function of the interacting continuum phenomena, i.e. free surface flow, heat transfer, and solidification, in complex three-dimensional geometries which allows to identify the distinction between surface depression, surface connected cavities and internal cavities.The model solves the coupled macroscopic conservation equations for mass, momentum, and energy with a phase change during solidification. In the model, the volume deficit due to solidification can either be compensated by depression of the outside surface or by creating a cavity that initiates either on the surface or in the interior of the casting. The solidification morphology is taken into account by using a parameter, which depends on the fraction solid, in the momentum equation. By using an adapted free surface algorithm, it is suitable to predict surface connected defects: depressed surfaces and caved surfaces. A critical pressure serves as a criterion to open internal shrinkage cavities. The model does not need to search for connected zones to feed shrinkage, but the shrinkage distribution will automatically emerge from the continuity equation.This advanced shrinkage model has experimentally been validated successfully using two Al-Si alloys, a skin freezing eutectic alloy and a mushy freezing hypo-eutectic alloy.     

实验室检测/校准方法的确认研究

结合实验室方法确认工作中的经验,从方法确认的内容、过程、结果以及记录的形成等方面,阐述了实验室方法确认工作有效开展的保障措施。     

Testing of a GIS model ofEucalyptus Iargiflorens health on a semiarid,saline floodplain

Irrigated agriculture has resulted in substantial changes in water flows to the lower reaches of the River Murray. These changes have led to large-scale occurrences of dieback inEucalyptus largiflorens (black box) woodlands as well as increased inputs of salt to the river. Management options to address problems of this scale call for the use of spatial data sets via geographic information systems (GIS). A GIS exists for one floodplain of the River Murray at Chowilla, and a simple model predicted six health classes ofEucalyptus largiflorens based on groundwater salinity, flooding frequency, and groundwater depth.To determine the usefulness of the model for vegetation management, the quality of both the model and the GIS data sets were tested. Success of the testing procedure was judged by the degree of spatial matching between the model's predictions of health and that assessed from aerial photographs and by field truthing. Analyses at 80 sites showed that tree health was significantly greater where groundwater salinity was less than 40 dS/m or flooding occurred more frequently than 1 in 10 years or depth to groundwater exceeded 4 m. Testing of the GIS data sets found that vegetation was misclassified at 15% of sites. Association was shown between GIS-predicted values and field-truthed values of groundwater salinity but not groundwater depth. The GIS model of health is a useful starting point for future vegetation management and can be further improved by increasing the quality of the data coverages and further refining of the model to optimize parameters and thresholds.     

Referee analyses: A better approach than data validation

Data validation, as prescribed in guidance documents provided by the United States Environmental Protection Agency (EPA), yields legal evidence that an analytical laboratory has performed analyses according to predetermined specifications. This validation process, because it involves only the checking of procedural documentation, provides minimal information concerning the technical validity of the data. Unfortunately, in the minds of many, the performance of such a data validation has become synonymous with technical validity. A better approach is to implement a routine program of referee analyses. That is, submit a predetermined number of samples from the project to a second laboratory. A routine program of this type provides a self-checking and self-correcting mechanism for determining whether data are technically valid. Publication No. 3874, Environmental Sciences Division, ORNL. Managed by Martin-Marietta Energy Systems, Inc. for the US Department of Energy under Contract No. DE-AC05-840R21400.     

Modeling of non-reactive solute transport in fractured clayey till during variable flow rate and time

Fractures and biopores can act as preferential flow paths in clay aquitards and may rapidly transmit contaminants into underlying aquifers. Reliable numerical models for assessment of groundwater contamination from such aquitards are needed for planning, regulatory and remediation purposes. In this investigation, high resolution preferential water-saturated flow and bromide transport data were used to evaluate the suitability of equivalent porous medium (EPM), dual porosity (DP) and discrete fracture/matrix diffusion (DFMD) numerical modeling approaches for assessment of flow and non-reactive solute transport in clayey till. The experimental data were obtained from four large undisturbed soil columns (taken from 1.5 to 3.5 m depth) in which biopores and channels along fractures controlled 96-99% of water-saturated flow. Simulating the transport data with the EPM effective porosity model (FRACTRAN in EPM mode) was not successful because calibrated effective porosity for the same column had to be varied up to 1 order of magnitude in order to simulate solute breakthrough for the applied flow rates between 11 and 49 mm/day. Attempts to simulate the same data with the DP models CXTFIT and MODFLOW/MT3D were also unsuccessful because fitted values for dispersion, mobile zone porosity, and mass transfer coefficient between mobile and immobile zones varied several orders of magnitude for the different flow rates, and because dispersion values were furthermore not physically realistic. Only the DFMD modeling approach (FRACTRAN in DFMD mode) was capable to simulate the observed changes in solute transport behavior during alternating flow rate without changing values of calibrated fracture spacing and fracture aperture to represent the macropores.