Effect of corn root exudates on the degradation of atrazine and its chlorinated metabolites in soils

DIMBOA (3,4-dihydro-2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), a major benzoxazinone of Poaceae plants, was isolated and purified from corn seedlings. The effect of isolated and purified DIMBOA on the degradation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine], and its toxic breakdown products, desethylatrazine [2-chloro-4-amino-6-(isopropylamino)-s-triazine; DEA] and desisopropylatrazine [2-chloro-4-(ethylamino)-6-amino-s-triazine; DIA], was studied in the absence of plants using batch experiments, while the effect of corn root exudates on these compounds was determined in hydroponic experiments. Degradation experiments were performed in the presence and absence of 50 microM, 1 mM, or 5 mM DIMBOA resulting in ratios of DIMBOA to pesticide of 1:1, 20:1, and 100:1. We observed a 100% degradation of atrazine to hydroxyatrazine within 48 h at a ratio of DIMBOA to atrazine of 100:1. DIMBOA had the largest effect on atrazine, while it was about three times less effective on DEA and DIA. Corn (Zea mays L. cv. LG 2185) was exposed to 10 mg L(-1) of either atrazine, DEA, or DIA for 11 d in a growth chamber experiment. Up to 4.3 micromol L(-1) d(-1) of hydroxyatrazine were formed in the nutrient solutions by plants exposed to atrazine, while the formation of hydroxylated metabolites from plants exposed to DEA and DIA was smaller and also delayed. The formation of hydroxylated metabolites increased in the solution with plant age in all atrazine, DEA, and DIA treatments. HMBOA (3,4-dihydro-2-hydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), the lactam precursor of DIMBOA, and a tentatively identified derivative of MBOA (2,3-dihydro-6-methoxy-benzoxazol-2-one) were detected in the corn root exudates. Mass balance calculations revealed that up to 30% of the disappearance of atrazine and DEA, and up to 10% of DIA removal from the solution medium in our study could be explained by the formation of hydroxylated metabolites in the solution itself. Our results show that higher plants such as corn have the potential to promote the hydrolysis of triazine residues in soils by exudation of benzoxazinones.     

Rapid removal of nitrate and sulfate in freshwater wetland sediments

Anaerobic microbial processes play particularly important roles in the biogeochemical functions of wetlands, affecting water quality, nutrient transport, and greenhouse gas fluxes. This study simultaneously examined nitrate and sulfate removal rates in sediments of five southwestern Michigan wetlands varying in their predominant water sources from ground water to precipitation. Rates were estimated using in situ push-pull experiments, in which 500 mL of anoxic local ground water containing ambient nitrate and sulfate and amended with bromide was injected into the near-surface sediments and subsequently withdrawn over time. All wetlands rapidly depleted nitrate added at ambient ground water concentrations within 5 to 20 h, with the rate dependent on concentration. Sulfate, which was variably present in porewaters, was also removed from injected ground water in all wetlands, but only after nitrate was depleted. The sulfate removal rate in ground water-fed wetlands was independent of concentration, in contrast to rates in precipitation-fed wetlands. Sulfate production was observed in some sites during the period of nitrate removal, suggesting that the added nitrate either stimulated sulfur oxidation, possibly by bacteria that can utilize nitrate as an oxidant, or inhibited sulfate reduction by stimulating denitrification. All wetland sediments examined were consistently capable of removing nitrate and sulfate at concentrations found in ground water and precipitation inputs, over short time and space scales. These results demonstrate how a remarkably small area of wetland sediment can strongly influence water quality, such as in the cases of narrow riparian zones or small isolated wetlands, which may be excluded from legal protection.     

Long-term effects of sustained beef feedlot manure application on soil nutrients, corn silage yield, and nutrient uptake

A field study was initiated in 1992 to investigate the long-term impacts of beef feedlot manure application (composted and uncomposted) on nutrient accumulation and movement in soil, corn silage yield, and nutrient uptake. Two application strategies were compared: providing the annual crop nitrogen (N) requirement (N-based rate) or crop phosphorus (P) removal (P-based rate), as well as a comparison to inorganic fertilizer. Additionally, effects of a winter cover crop were evaluated. Irrigated corn (Zea mays L.) was produced annually from 1993 through 2002. Average silage yield and crop nutrient removal were highest with N-based manure treatments, intermediate with P-based manure treatments, and least with inorganic N fertilizer. Use of a winter cover crop resulted in silage yield reductions in four of ten years, most likely due to soil moisture depletion in the spring by the cover crop. However, the cover crop did significantly reduce NO3-N accumulation in the shallow vadose zone, particularly in latter years of the study. The composted manure N-based treatment resulted in significantly greater soil profile NO3-N concentration and higher soil P concentration near the soil surface. The accounting procedure used to calculate N-based treatment application rates resulted in acceptable soil profile NO3-N concentrations over the short term. While repeated annual manure application to supply the total crop N requirement may be acceptable for this soil for several years, sustained application over many years carries the risk of unacceptable soil P concentrations.     

Effects of commercial diazinon and imidacloprid on microbial urease activity in soil and sod

Diazinon [O,O-diethyl O-2-isopropyl-6-methyl(pyrimidine-4-yl) phosphorothioate] and imidacloprid [1-(1-[6-chloro-3-pyridinyl]methyl)-N-nitro-2-imidazolidinimine] are applied to lawns for insect control simultaneously with nitrogenous fertilizers such as urea, but their potential effect on urease activity and nitrogen availability in turfgrass management has not been evaluated. Urease activity in enzyme assays, washed cell assays, and soil slurries was examined as a function of insecticide concentration. Intact cores from field sites were used to assess the effect of insecticide application on urease activity in creeping bentgrass (Agrostis palustris Huds.) and bluegrass (Poa pratensis L.) sod. Bacterial urease from Bacillus pasteurii and plant urease from jack bean [Canavalia ensiformis (L.) DC.] were unaffected by the insecticides. Both insecticides inhibited the growth of Proteus vulgaris, a urease-producing bacterium, but only diazinon significantly reduced urease activity in washed cells; neither insecticide inhibited urease activity in sonicated cells. Neither diazinon nor imidacloprid inhibited urease activity in Woolper soil (fine, mixed, mesic Typic Argiudoll) slurries, but diazinon slightly inhibited urease activity in Maury soil (fine, mixed, semiactive, mesic Typic Paleudalf) slurries. Imidacloprid had no effect on urease activity in creeping bentgrass or bluegrass sod at up to 10 times the commercial application rate. Diazinon briefly, but significantly, reduced urease activity in bluegrass sod. Co-application of imidacloprid and urea appears to be benign with respect to urease activity in soil and sod. Diazinon, in contrast, appears to have a significant, short-term, inhibitory effect on the microbial urease-producing community, but that effect depends on soil type.     

Influence of canola and sunflower diet amendments on cattle feedlot manure

Cattle (Bos taurus) producers can replace a part of the traditional diet of barley (Hordeum vulgare L.) grain/silage with sunflower (Helianthus annus L.) seeds or canola meal (Brassica napus L.)/oil to enhance conjugated linoleic acids (CLA) content in milk and meat for its positive health benefits. The objective of this study is to investigate the effects of feeding sunflower or canola to finishing steers on cattle manure chemical properties and volatile fatty acid (VFA) content. The control diet contained 84% rolled barley and 15% barley silage, which provided only 2.6% lipid. The other six treatments had 6.6 to 8.6% lipid delivered from sources such as hay, sunflower seed (SS), canola meal/oil, and SS forage pellets. Manure samples (a mixture of cattle urine, feces, and woodchip bedding materials) were collected and analyzed after cattle had been on these diets for 113 d. The dietary source and level of lipid had no effect on organic N and nitrate N content in manure, but significantly affected ammonia N and VFA. Inclusion of SS forage pellets, hay, or canola meal/oil in cattle diets had no significant impact on manure characteristics, but SS significantly reduced the pH and increased propionic, isobutyric, and isovaleric content. In addition, N loss after excretion (mainly from urine N) increases with the pH and N levels in both feed and manure. The combination of SS with barley silage resulted in a lower VFA and NH3 content in manure and should be a more attractive option. To better manage N nutrient cycles and reduce NH3 related odor problems, feed and manure pH should be one of the factors to consider when determining feed mix rations.     

Accelerated soil dissipation of tebuconazole following multiple applications to peanut

Repeated application may increase rates of pesticide dissipation in soil and reduce persistence. The potential for this to occur was investigated for the fungicide, tebuconazole (alpha-[2-(4-chlorophenyl)ethyl]-alpha-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol), when used for peanut (Arachis hypogaea L.) production. Soil samples were collected from peanut plots after each of four tebuconazole applications at 2-wk intervals. Soil moisture was adjusted to field capacity as necessary and samples were incubated in the laboratory for 63 d at 30 degrees C. Untreated plot samples spiked with the compound served as controls. Results indicated accelerated dissipation in field-treated samples with the time to fifty percent dissipation (DT50) decreasing from 43 to 5 d after three tebuconazole applications. Corresponding increases in rates of accumulation and decay of degradates were also indicated. Best-fit equations (r2 = 0.84-0.98) to dissipation kinetic data combined with estimates of canopy interception rates were used to predict tebuconazole and degradates concentration in soil after each successive application. Predicted concentrations compared with values measured in surface soil samples were from twofold less to twofold greater. Use of kinetic data will likely enhance assessments of treatment efficacy and human and ecological risks from normal agronomic use of tebuconazole on peanut. However, the study indicated that varying soil conditions (in particular, soil temperature and water content) may have an equal or greater impact on field dissipation rate than development of accelerated dissipation. Results emphasize that extension of laboratory-derived kinetic data to field settings should be done with caution.     

Green roof stormwater retention: effects of roof surface, slope, and media depth

Urban areas generate considerably more stormwater runoff than natural areas of the same size due to a greater percentage of impervious surfaces that impede water infiltration. Roof surfaces account for a large portion of this impervious cover. Establishing vegetation on rooftops, known as green roofs, is one method of recovering lost green space that can aid in mitigating stormwater runoff. Two studies were performed using several roof platforms to quantify the effects of various treatments on stormwater retention. The first study used three different roof surface treatments to quantify differences in stormwater retention of a standard commercial roof with gravel ballast, an extensive green roof system without vegetation, and a typical extensive green roof with vegetation. Overall, mean percent rainfall retention ranged from 48.7% (gravel) to 82.8% (vegetated). The second study tested the influence of roof slope (2 and 6.5%) and green roof media depth (2.5, 4.0, and 6.0 cm) on stormwater retention. For all combined rain events, platforms at 2% slope with a 4-cm media depth had the greatest mean retention, 87%, although the difference from the other treatments was minimal. The combination of reduced slope and deeper media clearly reduced the total quantity of runoff. For both studies, vegetated green roof systems not only reduced the amount of stormwater runoff, they also extended its duration over a period of time beyond the actual rain event.     

Rapid manganese removal from mine waters using an aerated packed-bed bioreactor

In the UK, the Environmental Quality Standard for manganese has recently been lowered to 30 microg/L (annual average), which is less than the UK Drinking Water Inspectorate's Maximum Permitted Concentration Value (50 microg/L). Current passive treatment systems for manganese removal operate as open-air gravel-bed filters, designed to maximize either influent light and/or dissolved oxygen. This requires large areas of land. A novel enhanced bioremediation treatment system for manganese removal has been developed that consists of a passively aerated subsurface gravel bed. The provision of air at depth and the use of catalytic substrates help overcome the slow kinetics usually associated with manganese oxidation. With a residence time of only 8 h and an influent manganese concentration of approximately 20 mg/L, >95% of the manganese was removed. The treatment system also operates successfully at temperatures as low as 4 degrees C and in total darkness. These observations have positive implications for manganese treatment using this technique in both colder climates and where large areas of land are unavailable. Furthermore, as the operation of this passive treatment system continually generates fresh manganese oxyhydroxide, which is a powerful sorbent for most pollutant metals, it potentially has major ancillary benefits as a removal process for other metals, such as zinc.     

Macroinvertebrate communities in agriculturally impacted southern Illinois streams: patterns with riparian vegetation, water quality, and in-stream habitat quality

Relationships between riparian land cover, in-stream habitat, water chemistry, and macroinvertebrates were examined in headwater streams draining an agricultural region of Illinois. Macroinvertebrates and organic matter were collected monthly for one year from three intensively monitored streams with a gradient of riparian forest cover (6, 22, and 31% of riparian area). Bioassessments and physical habitat analyses were also performed in these three streams and 12 other nearby headwater streams. The intensively monitored site with the least riparian forest cover had significantly greater percent silt substrates than the sites with medium and high forest cover, and significantly higher very fine organics in substrates than the medium and high forested sites. Macroinvertebrates were abundant in all streams, but communities reflected degraded conditions; noninsect groups, mostly oligochaetes and copepods, dominated density and oligochaetes and mollusks, mostly Sphaerium and Physella, dominated biomass. Of insects, dipterans, mostly Chironomidae, dominated density and dipterans and coleopterans were important contributors to biomass. Collector-gatherers dominated functional structure in all three intensively monitored sites, indicating that functional structure metrics may not be appropriate for assessing these systems. The intensively monitored site with lowest riparian forest cover had significantly greater macroinvertebrate density and biomass, but lowest insect density and biomass. Density and biomass of active collector-filterers (mostly Sphaerium) decreased with increasing riparian forest. Hilsenhoff scores from all 15 sites were significantly correlated with in-stream habitat scores, percent riparian forest, and orthophosphate concentrations, and multiple regression indicated that in-stream habitat was the primary factor influencing biotic integrity. Our results show that these "drainage ditches" harbor abundant macroinvertebrates that are typical of degraded conditions, but that they can reflect gradients of conditions in and around these streams.     

Simple models for phosphorus loss from manure during rainfall

Mechanistic, predictive equations for phosphorus (P) transport in runoff from manure-applied fields constitute a critical knowledge gap for developing nonpoint-source pollution models. We derived two simple equations to describe the P release from animal manure during a rainfall event-one based on first-order P desorption kinetics and one based on second-order kinetics. The manure characteristics needed in the two kinetic equations are the maximum amount of water-extractable phosphorus (WEP) and a characteristic desorption time. Water-extractable P can be measured directly but currently the characteristic time can only be obtained by fitting experimental data. In addition, we evaluated two models usually used to estimate P loss from soil, the Elovitch equation and power function, both of which relate P loss to time. The models were tested against previously published data of P release from different manures under laboratory conditions. All equations fit the data well. Of the two kinetic equations, the second-order model showed better agreement with the data than the first-order model; for example, maximum relative differences between the model results and measured data were 2.6 and 4.7%, respectively. The characteristic times varied between 20 min for dairy manure and almost 100 min for poultry manure. The characteristic time did not appear to change with flow rate but decreased with smaller manure aggregates. The parameters for power-function relationships could not be related to measured manure characteristics. These results provide the first step to process-based approximations for predicting P release from manure with time during rainfall shortly after land application, when P losses are the greatest.