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.     

Effects of Acidification and its Mitigation with Lime and Wood Ash on Forest Soil Processes: A Review

Anthropogenic acid deposition causes forest soil acidification and perturbation of the soil forming processes. The impact of soil acidification on tree growth is discussed in view of the role of mycorrhizal fungi in weathering and nutrient uptake. A review has been carried out of experiments involving treatments of forest soil by lime and wood ash, where soil properties and soil solution composition have been investigated. Results from these experiments in Europe and North America are summarized. In general, the content of C in the mor layer decreased as a result of treatment due to higher microbial activity and soil respiration as well as increased leakage of DOC. In addition, the content of N in the mor layer, in general, decreased after treatment and there are occasional peaks of high NO₃concentrations in soil solution. In nearly all reviewed investigations the pH of the deep mineral soil solution decreased and Al, SO₄and NO₃concentrations increased after treatment. These effects are probably due to the high ionic strength and increased microbial activity as a consequence of the treatments. In the soil, pH, CEC and base saturation increased in the upper horizons, but decreases in the upper mineral soil are also reported. In general, there was no increase in tree growth as a result of these treatments. The positive effects of the treatments on soil processes and tree growth are therefore questionable. In view of these conclusions, an investigation was carried out on the soil and soil solution chemistry and the role of mycorrhizal fungi in a spruce stand treated with two doses of lime and another treated with lime/ash in southern Sweden. The results of this investigation is reported in this volume.     

Development of a procedure for sustainable in situ aquifer denitrification

Denitrification experiments have provided data showing the pitfalls and successes in developing a sustainable injection/extraction system in a sand and gravel aquifer. Experiments increase in complexity from continuous injection at one well to automated‐pulsed eight well injections. In both continuous and pulsed injection of organic carbon, 40 mg NO_3‐N l^?1 was reduced below the detection limit of < 0.1 mg NO_3‐N l^?1 in the denitrification zones. Under continuous injection, accumulation of bacterial exudates in the vicinity of the injection well resulted in injection well clogging within ten days. Periodic cleaning of the injection well and the adjacent gravel matrix was accomplished by using a tool developed to circulate a cleaning solution composed of 5 percent H₂O₂ and 0.02 percent NaOCl; but, biofouling could not be eliminated. In the later experiments, acetate became the carbon amendment because ethanol promoted more biomass development. A specialized pulse injection procedure was developed to separate nitrate from acetate‐C and was successful in alleviating the proliferation of bacterial exudates without affecting the performance of the denitrification system. Using pulsed injection, a maximum of 72 percent nitrate reduction was accomplished in the extraction well water, and denitrification was sustained for three months without clogging. © 2003 Wiley Periodicals, Inc.     

Treatment of chromium plating process effluents with ion exchange resins.

The surface treatment industry deals with various heavy metals, including the elements Cr, Zn, Ni, Cd, and Cu. Conventional treatments of effluents generate class I solid residue. The aim of this investigation was to study the viability of ion exchange as an alternative process for treatment of rinse water and to determine the efficacy of two ion exchange systems, System 1: "strong" cationic resin-"strong" anionic resin and System 2: "strong" cationic resin-"weak" anionic resin. Commercial resins and solutions taken from rinse tanks of chromium plating companies were used in this investigation. A two-column system, one for the cationic resin and another for the anionic resin, both with 150 ml capacity was mounted. The solution was percolated at a rate of 10 ml/min. The following solutions were used for regeneration of the resins: 2% H2SO4 for the cationic and 4% NaOH for the anionic. The percolated solutions revealed chromium contents of less than 0.25 mg/l, independent of the system used. The "strong" cationic resin-"weak" anionic resin gave excellent regeneration results. The "strong" cationic-"strong" anionic resin presented problems during regeneration, and did not release the retained ions after percolation of 2000 ml of 4% NaOH solution. It is concluded that for this type of treatment, the system composed of "strong" cationic resin and "weak" anionic resin is more appropriate.     

Estimation of odor emission rate from landfill areas using the sniffing team method

The monitoring of the odor annoyance generated by a landfill area is difficult, since it is a multi-area-sources problem, with a discontinuous odor emission. This paper proposes an adaptation of the method of sniffing team campaigns to the particular case of fresh waste odors. The method is based on the field determination of odor perception points, followed by data processing with a bi-Gaussian-type model, adapted to handle the odors. In a first step, field observers delineate the region in which odor impact is experienced and then the emission rate is manipulated in a dispersion model until the predicted size of the impact zone matches that observed in the field. In a second step the adjusted emission rate is entered into the model to calculate the percentiles corresponding to the average annoyance zone. The originality of the proposed method is the introduction of all observation points and of all recorded meteorological data into the model. The paper discusses the method limitations and the errors induced on the results, i.e. the odor emission rate and the percentile lines (or iso-concentration lines) which are used to describe the odor concentrations on a map of the surroundings of the plant. The proposed method proves to be reliable for diffuse sources, such as landfill areas. The obtained results are coherent with other results found in the literature with other techniques.     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Effect of low-molecular weight organic acids on phosphorus release and phytoavailabilty of phosphorus in phosphate rocks added to soils

Phosphorus (P) is critically needed to improve soil fertility in many parts of the world. The use of water-soluble P fertilizers, e.g., single super-phosphate and triple super-phosphate in developing countries to improve crop production has been limited primarily by their high cost. The presence of indigenous phosphate deposits in some countries provides an incentive for direct application or local chemical treatment at low cost to improve the solubility of low reactive phosphate rocks (PRs). The use of naturally occurring low-molecular weight organic acids (LMWOAs) that are produced in soil as microbial metabolites or plant exudates from dead or living cells represents a new perspective in PR research. The LMWOAs contain various functional groups that may play a significant role in PR dissolution. Little information is available, however, about the potential of LMWOAs in releasing P from PRs. This study reports P release from 12 PRs, four each of low, medium, and high reactivity, obtained from various deposits (Kodjari, Tahoua, North Carolina, Gafsa, Khouribga, Tilemsi Valley, Central Florida, Sechura, Minjingu, North Florida, Hahotoe, and Parc W) using nine LMWOAs containing mono-, di-, and tri-carboxylic groups and a mineral acid (H₂SO₄). Laboratory studies showed that the organic acids are effective in releasing P from low and medium reactive PRs, but very ineffective in releasing P from high reactive PRs. The average amounts of P released by all the organic acids from the three types of PRs were 65.5 mmol kg⁻¹ PR from the low reactive PRs, 55.1 mmol kg⁻¹ from the medium, and 11.1 mmol kg⁻¹ from the high; those released from across all the PRs were 21.9 by the mono-carboxylic acid group, 54.2 by the di-carboxylic acid group, and 57.0 mmol P kg⁻¹ by the tri-carboxylic acid group. The P released was negatively correlated with the equilibrium pH, but positively correlated with Ca released from the PRs. Laboratory incubation studies on the release of P from PRs added to soils with or without organic acids and incubated at 25 °C for 15, 30, and 45 days showed that the percentage of plant-available P released varied considerably from 0.95 in the Kodjari PR to 40.1% in the North Carolina PR and was related to PR reactivity. A greenhouse study with corn (Zea mays L.) grown for 60 days on soils treated with PRs or with PRs mixed with organic acids showed that corn response to addition of oxalic or citric acid varied with P rates and PR sources, suggesting that organic acids have potential as amendments for increasing plant-available P in PR-treated soils.     

Protozoan colonization on artificial substrates in relation to water quality in a tropical Indian harbour.

A field study was conducted to evaluate the protozoan colonization patterns on artificial substrates in relation to organic pollution within a tropical harbour. The composition of protozoans and their succession rates on artificial substrates(polyurethane foam units) were compared between two field stations(A and B), and their presence were considered with regards to the prevailing water quality conditions at the study sites. Altogether 44 genera of flagellates and ciliates were documented. The common genera of flagellates encountered included Monas, Polytoma, and Chromalina. Among the ciliates, the predominant genera were Tetrahymena, Vorticella, Lagymophyra, and Heloiphyra. These groups exhibited characteristic successional patterns in relation to ambient water quality. At Station A, located close to the sewage outfall, the water quality parameters included poor Secchi-disc transparency(0.48 m), dissolved oxygen of 1.93 mg/ml, salinity of 18 psu, and temperature 31.3 degrees C. Here, the nanoflagellates (spumella) colonized first, followed by microcilliate(Tetrahymena) and sessile form(Vorticella). Station B, located on the seaward side, was characterized by relatively less-stressed environmental conditions with transparency 1.85 m and dissolved oxygen value of 6.04 mg/ml. Salinity of 27.27 psu, and mean temperature of 30 degrees C were recorded at "B". At this station, the nanoflagellate Polytoma was first documented to colonize on the substrates, followed by microcilliate(Lagynophrya) and suctorid(Heliophyra). These findings support the use of protozoans as indicator species for evaluating the hazards posed by organic pollution to natural estuarine communities.