Modeling Parent and Metabolite Fate and Transport in Subsurface Drained Fields With Directly Connected Macropores1

Abstract: Few studies exist that evaluate or apply pesticide transport models based on measured parent and metabolite concentrations in fields with subsurface drainage. Furthermore, recent research suggests pesticide transport through exceedingly efficient direct connections, which occur when macropores are hydrologically connected to subsurface drains, but this connectivity has been simulated at only one field site in Allen County, Indiana. This research evaluates the Root Zone Water Quality Model (RZWQM) in simulating the transport of a parent compound and its metabolite at two subsurface drained field sites. Previous research used one of the field sites to test the original modification of the RZWQM to simulate directly connected macropores for bromide and the parent compound, but not for the metabolite. This research will evaluate RZWQM for parent/metabolite transformation and transport at this first field site, along with evaluating the model at an additional field site to evaluate whether the parameters for direct connectivity are transferable and whether model performance is consistent for the two field sites with unique soil, hydrologic, and environmental conditions. Isoxaflutole, the active ingredient in BALANCE^® herbicide, was applied to both fields. Isoxaflutole rapidly degrades into a metabolite (RPA 202248). This research used calibrated RZWQM models for each field based on observed subsurface drain flow and/or edge of field conservative tracer concentrations in subsurface flow. The calibrated models for both field sites required a portion (approximately 2% but this fraction may require calibration) of the available water and chemical in macropore flow to be routed directly into the subsurface drains to simulate peak concentrations in edge of field subsurface drain flow shortly after chemical applications. Confirming the results from the first field site, the existing modification for directly connected macropores continually failed to predict pesticide concentrations on the recession limbs of drainage hydrographs, suggesting that the current strategy only partially accounts for direct connectivity. Thirty‐year distributions of annual mass (drainage) loss of parent and metabolite in terms of percent of isoxaflutole applied suggested annual simulated percent losses of parent and metabolite (3.04 and 1.31%) no greater in drainage than losses in runoff on nondrained fields as reported in the literature.     

Characterisation of polycyclic aromatic hydrocarbons in flue gas and residues of a full scale fluidized bed combustor combusting non-hazardous industrial waste

This paper studies the fate of PAHs in full scale incinerators by analysing the concentration of the 16 EPA-PAHs in both the input waste and all the outputs of a full scale Fluidized Bed Combustor (FBC). Of the analysed waste inputs i.e. Waste Water Treatment (WWT) sludge, Refuse Derived Fuel (RDF) and Automotive Shredder Residue (ASR), RDF and ASR were the main PAH sources, with phenanthrene, fluoranthene and pyrene being the most important PAHs. In the flue gas sampled at the stack, naphthalene was the only predominant PAH, indicating that the PAHs in FBC’s combustion gas were newly formed and did not remain from the input waste. Of the other outputs, the boiler and fly ash contained no detectable levels of PAHs, whereas the flue gas cleaning residue contained only low concentrations of naphthalene, probably adsorbed from the flue gas. The PAH fingerprint of the bottom ash corresponded rather well to the PAH fingerprint of the RDF and ASR, indicating that the PAHs in this output, in contrast to the other outputs, were mainly remainders from the PAHs in the waste inputs. A PAH mass balance showed that the total PAH input/output ratio of the FBC ranged from about 100 to about 2600 depending on the waste input composition and the obtained combustion conditions. In all cases, the FBC was clearly a net PAH sink.     

VALIDATION OF A BRIEF SCREENING MEASURE OF ENVIRONMENTAL CHEMICAL SENSITIVITY: THE CHEMICAL ODOR INTOLERANCE INDEX

The development and validation of a brief self-report screening measure of environmental chemical sensitivity, the Chemical Odor Intolerance Index (CII), is described. Subjects included 1734 college students, 192 older adults, and 38 chemically intolerant and multiple chemical sensitivity (MCS) patients. The results of the studies demonstrate that the CII has strong internal stability (Cronbach's alpha ranging from 0.80 to 0.92 across samples), and evidence of factorial, group, convergent, and discriminant validity is reported across diverse samples. In future research, the CII will permit the quantification of self-reported illness from low levels of environmental chemicals as a continuous rather than dichotomous variable. Consequently, the CII will facilitate the ability to compare and standardize subject selection criteria in both preclinical and clinical (i.e. MCS) populations.     

Using Satellite Imagery to Assess Large-Scale Habitat Characteristics of Adirondack Park, New York, USA

Satellite imagery is a useful tool for large-scale habitat analysis; however, its limitations need to be tested. We tested these limitations by varying the methods of a habitat evaluation for white-tailed deer (Odocoileus virginianus) in the Adirondack Park, New York, USA, utilizing harvest data to create and validate the assessment models. We used two classified images, one with a large minimum mapping unit but high accuracy and one with no minimum mapping unit but slightly lower accuracy, to test the sensitivity of the evaluation to these differences. We tested the utility of two methods of assessment, habitat suitability index modeling, and pattern recognition modeling. We varied the scale at which the models were applied by using five separate sizes of analysis windows. Results showed that the presence of a large minimum mapping unit eliminates important details of the habitat. Window size is relatively unimportant if the data are averaged to a large resolution (i.e., township), but if the data are used at the smaller resolution, then the window size is an important consideration. In the Adirondacks, the proportion of hardwood and softwood in an area is most important to the spatial dynamics of deer populations. The low occurrence of open area in all parts of the park either limits the effect of this cover type on the population or limits our ability to detect the effect. The arrangement and interspersion of cover types were not significant to deer populations.     

ENHANCEMENTS OF NONPOINT SOURCE MONITORING OF VOLATILE ORGANIC COMPOUNDS IN GROUND WATER1

ABSTRACT: The U.S. Geological Survey (USGS) has compiled a national retrospective data set of analyses of volatile organic compounds (VOCs) in ground water of the United States. The data are from Federal, State, and local nonpoint‐source monitoring programs, collected between 1985–95. This data set is being used to augment data collected by the USGS National Water‐Quality Assessment (NAWQA) Program to ascertain the occurrence of VOCs in ground water nationwide. Eleven attributes of the retrospective data set were evaluated to determine the suitability of the data to augment NAWQA data in answering occurrence questions of varying complexity. These 11 attributes are the VOC analyte list and the associated reporting levels for each VOC, well type, well‐casing material, type of openings in the interval (screened interval or open hole), well depth, depth to the top and bottom of the open interval(s), depth to water level in the well, aquifer type (confined or unconfined), and aquifer lithology. VOCs frequently analyzed included solvents, industrial reagents, and refrigerants, but other VOCs of current interest were not frequently analyzed. About 70 percent of the sampled wells have the type of well documented in the data set, and about 74 percent have well depth documented. However, the data set generally lacks documentation of other characteristics, such as well‐casing material, information about the screened or open interval(s), depth to water level in the well, and aquifer type and lithology. For example, only about 20 percent of the wells include information on depth to water level in the well and only about 14 percent of the wells include information about aquifer type. The three most important enhancements to VOC data collected in nonpoint‐source monitoring programs for use in a national assessment of VOC occurrence in ground water would be an expanded VOC analyte list, recording the reporting level for each analyte for every analysis, and recording key ancillary information about each well. These enhancements would greatly increase the usefulness of VOC data in addressing complex occurrence questions, such as those that seek to explain the reasons for VOC occurrence and nonoccurrence in ground water of the United States.     

THE IMPACT OF URBANIZATION ON THE DISTRIBUTION OF HEAVY METALS IN BOTTOM SEDIMENTS OF THE SADDLE RIVER1

ABSTRACT: A three-year study has been conducted on a 4.6 mile stretch of the Saddle River near Lodi, New Jersey. The primary objectives of this investigation were (1) to provide baseline information on the concentration and distribution of heavy metals in bottom sediments of the Saddle River; (2) to qualitatively evaluate which parameters affect this distribution; and (3) to determine the effect of urbanization on the concentration and distribution of these materials. Significant enrichments of several heavy metals were observed in bottom sediments of the lower Saddle River near Lodi, New Jersey, as compared to the upper Saddle River. Attempts to correlate metal concentrations in bottom sediments with chemical-oxygen demand were not successful in demonstrating a relationship between these two factors. Metal concentrations were found to be strongly dependent upon particle size. In general, metal concentrations in bottom sediments increased with decreasing partical diameter. However, metals enrichment was observed to be considerably greater in the larger sediment fractions studied (>420μ) than the smaller sediment fractions as one proceeded downstream through the urban area. Since the larger sediment fractions are least effected by scour and transport they may best reflect the effect of urbanization on the distribution of heavy metals over an extended period of time at a given location.     

Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

SUSPENDED SEDIMENT AND METALS REMOVAL FROM URBAN RUNOFF BY A SMALL LAKE1

ABSTRACT: A small lake in the Chicago Metropolitan Area was from 91 to 95 percent efficient in removing suspended sediment and from 76 to 94 percent efficient in removing copper, iron, lead, and zinc from urban runoff. Sediments accumulated in the lake in the form of an organic-rich mud at an average rate of 20 millimeters per year; this reduced lake storage and covered potential habitat for aquatic organisms. Copper, lead, and zinc concentrations were closely associated with suspended-sediment concentrations and with silt- and clay-sized fractions of lake sediment. Although concentrations of mercury and cadmium were near detection limits in runoff, measurable concentrations of these metals accumulated in the lake sediments.