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.     

DDT in fish from the Bulgarian region of the Black Sea

In spite of a worldwide reduction in the utilization of organochlorine pesticides (OCPs), they are still a problem for the aquatic environment and human health. The Black Sea is still being polluted with persistent chemicals, including OCPs. Aquatic organisms (sprat, scad, bluefish, shad, belted bonito, goby, and black mussel) with different feeding behaviours were sampled on a seasonal basis from the Bulgarian region of the Black Sea, and the concentrations of 13 OCP residues were determined. Although many of the OCPs were not detected in the samples, in all samples 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) was present mainly in the form of its metabolites 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDE). Only about 12% of the total DDT was present as the parent compound pp-DDT, which suggests that it was not being used recently in the region. The total DDT concentrations were generally below 150 μg kg^-1 fresh weight, but higher levels—up to 354 μg kg^-1 fresh weight—were also measured for fish species with a high fat content. Between-species differences were observed, even when the concentrations were presented on a fat-level basis. DDT concentrations did not show any significant changes over the 2-yr sampling period. Fish sampled in the northern areas of the Bulgarian Black Sea coast seemed to contain higher DDT levels than those from the southern areas, suggesting a major (historical) influence of the Danube River. For permanent monitoring purposes, the utility of Black Sea gobies and scad should be considered.     

Estimates of animal methane emissions

The enteric methane emissions into the atmospheric annually from domestic animals total about 77 Tg. Another 10 to 14 Tg are likely released from animal manure disposal systems. About 95% of global animal enteric methane is from ruminants, a consequence of their large populations, body size and appetites combined with the extensive degree of anaerobic microbial fermentation occurring in their gut. Accurate methane estimates are particularly sensitive to cattle and buffalo census numbers and estimated diet consumption. Since consumption is largely unknown and must be predicted, accuracy is limited often by the information required, i.e., distribution of animals by class, weight and productivity. Fraction of the diet lost as enteric methane mostly falls into the range of 5.5–6.5% of gross energy intake for the world's cattle, sheep and goats. Manure methane emissions are heavily influenced by fraction of disposal by anaerobic lagoon. Non-ruminants, i.e., swine, become major contributors to these emissions.     

Effect of periphyton grazing by Hydrobia ulvae on the growth of Zostera noltii on a tidal flat in the Dutch Wadden Sea

The decrease of the intertidal seagrass Zostera noltii in the Dutch Wadden Sea may have been the result of enhanced periphyton load due to eutrophication. Decrease of this seagrass species coincided with an increase in the mudsnail Hydrobia ulvae. Feeding of this mudsnail on periphyton may have partly counteracted an increase of periphyton biomass. Exclosure experiments on seagrass stands in the Dutch Wadden Sea in 1987 showed that density of periphyton on leaves of Z. noltii decreased significantly with increasing density of grazers. An increased density of mudsnails significantly enhanced the density and biomass of seagrass, in particular of the below ground parts. Since this seagrass species survives winter in temperate climate zones mainly by means of rhizomes, grazing may also influence the seagrass dynamics in the long term. Results of the experiment were in agreement with field observations on coinciding low densities of mudsnails and high densities of fouling of seagrass stands on the tidal flats of western Wadden Sea in the late 1970s.     

Inhibitory effects of red algal extracts on larval settlement of the barnacle Balanus improvisus

We examined the chemical antifouling properties of four sublittoral red algae, Chondrus crispus, Delesseria sanguinea, Osmundea ramosissima, and Polyides rotundus, which are all rarely fouled in the field. Two different approaches were used. Firstly, we tested the effects of lipophilic crude extracts on the settlement behaviour of cyprid larvae of the co-existing barnacle Balanus improvisus. Secondly, in a settlement preference experiment, we tested whether B. improvisus cyprid larvae settle on living algae when given a choice between natural algal surfaces and control surfaces. With this procedure, we were able to test both if the algae inhibit recruitment of cyprids, and if this inhibition is a result of chemistry. The settlement of B. improvisus larvae was strongly inhibited at concentrations estimated to be potentially ecologically relevant for all of the tested extracts. However, only C. crispus significantly inhibited settlement in the preference experiment, even though there was also a tendency for settlement inhibition on P. rotundus and O. ramosissima. In contrast, D. sanguinea seemed to stimulate settlement. This contradiction probably resulted from an extraction of metabolites that naturally occur only inside the alga. However, as this study shows, a combination of settlement assays with whole-cell extracts and preference tests of ecologically relevant fouling organisms on natural algal and control surfaces may be a useful procedure to avoid erroneous conclusions regarding natural antifouling roles of compounds based on settlement assays with only whole-cell extracts. Furthermore, this study also shows that production of inhibitory metabolites may explain the low degree of fouling, especially by B. improvisus, on C. crispus.Communicated by L. Hagerman, Helsingør