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.     

Quantifying the impact of regular cutting on vegetative buffer efficacy for nitrogen-15 sequestration

This study used the stable 15N isotope to quantitatively examine the effects of cutting on vegetative buffer uptake of NO3(-)-N based on the theory that regular cutting would increase N demand and sequestration by encouraging new plant growth. During the summer of 2002, 10 buffer plots were established within a flood-irrigated pasture. In 2003, 15N-labeled KNO3 was applied to the pasture area at a rate of 5 kg N ha(-1) and 99.7 atom % 15N. One-half of the buffer plots were trimmed monthly. In the buffers, the cutting effect was not significant in the first few weeks following 15N application, with both the cut and uncut buffers sequestering 15N. Over the irrigation season, however, cut buffers sequestered 2.3 times the 15N of uncut buffers, corresponding to an increase in aboveground biomass following cutting. Cutting and removing vegetation allowed the standing biomass to take advantage of soil 15N as it was released by microbial mineralization. In contrast, the uncut buffers showed very little change in 15N sequestration or biomass, suggesting senescence and a corresponding decrease in N demand. Overall, cutting significantly improved 15N attenuation from both surface and subsurface water. However, the effect was temporally related, and only became significant 21 to 42 d after 15N application. The dominant influence on runoff water quality from irrigated pasture remains irrigation rate, as reducing the rate by 75% relative to the typical rate resulted in a 50% decrease in total runoff losses and a sevenfold decrease in 15N concentration.     

Runoff phosphorus losses from surface-applied biosolids

Runoff losses of dissolved and particulate phosphorus (P) may occur when rainfall interacts with manures and biosolids spread on the soil surface. This study compared P levels in runoff losses from soils amended with several P sources, including 10 different biosolids and dairy manure (untreated and treated with Fe or Al salts). Simulated rainfall (71 mm h(-1)) was applied until 30 min of runoff was collected from soil boxes (100 x 20 x 5 cm) to which the P sources were surfaced applied. Materials were applied to achieve a common plant available nitrogen (PAN) rate of 134 kg PAN ha(-1), resulting in total P loading rates from 122 (dairy manure) to 555 (Syracuse N-Viro biosolids) kg P ha(-1). Two biosolids produced via biological phosphorus removal (BPR) wastewater treatment resulted in the highest total dissolved phosphorus (13-21.5 mg TDP L(-1)) and total phosphorus (18-27.5 mg TP L(-1)) concentrations in runoff, followed by untreated dairy manure that had statistically (p = 0.05) higher TDP (8.5 mg L(-1)) and TP (10.9 mg L(-1)) than seven of the eight other biosolids. The TDP and TP in runoff from six biosolids did not differ significantly from unamended control (0.03 mg TDP L(-1); 0.95 mg TP L(-1)). Highest runoff TDP was associated with P sources low in Al and Fe. Amending dairy manure with Al and Fe salts at 1:1 metal-to-P molar ratio reduced runoff TP to control levels. Runoff TDP and TP were not positively correlated to TP application rate unless modified by a weighting factor reflecting the relative solubility of the P source. This suggests site assessment indices should account for the differential solubility of the applied P source to accurately predict the risk of P loss from the wide variety of biosolids materials routinely land applied.     

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.     

Phosphorus leaching in sandy outwash soils following potato-processing wastewater application

Land application of wastewater presents potential for ground water pollution if not properly managed. In situ breakthrough tests were conducted using potato (Solanum tuberosum L.)-processing wastewater and a Br tracer to characterize P leaching in seasonally frozen sandy outwash soils. In the first test, P and Br breakthrough were measured in a 7-m deep well following wastewater [2.94 mg L(-1) total P (TP); 280 mg L(-1) Br] application at the site that had 13.1 mg water-extractable P (WEP) kg(-1)and 94.4 mg Bray-1 P kg(-1). Bromide was detected in the well after approximately 0.4 pore volumes, but there was no P break-through after 7 pore volumes. In the second breakthrough test, wastewater containing 3.6 mg L(-1) TP and 259 mg L(-1) Br was applied on 1.5-m deep lysimeters at low (0.8 mg WEP kg(-1); 12.1 mg Bray-1 P kg(-1)) and high soil test P sites (104 mg WEP kg(-1); 585 mg Bray-1 P kg(-1)). Leachate TP concentration during the test remained constant (0.04 mg L(-1)) at the low P sites but increased from approximately 3.5 to 5.6 mg L(-1) at the high P sites. These results indicate no P leaching in low P soils, but leaching in high P soils, thus suggesting that most of the P leached at the high P sites was mainly due to desorption and dissolution of weakly adsorbed P from prior P applications. This was consistent with P transport simulations using the convective-dispersive equation. We conclude that P concentration in land-applied wastewater should be regulated based on soil test-P level plus wastewater P loading.     

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.     

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.     

FOREST HARVESTING AND STREAMWATER INORGANIC CHEMISTRY IN WESTERN NORTH AMERICA: A REVIEW1

The solution chemistry of forested streams primarily in western North America is explained by considering the major factors that influence this chemistry — geological weathering; atmospheric precipitation and climate; precipitation acidity; terrestrial biological processes; physical/chemical reactions in the soil; and physical, chemical, and biological processes within streams. Due to the complexity of all these processes and their varying importance for different chemicals, stream water chemistry has exhibited considerable geographic and temporal variation and is difficult to model accurately. The impacts of forest harvesting on stream water chemistry were reviewed by considering the effects of harvesting on each of the important factors controlling this chemistry, as well as other factors influencing these impacts ‐ extent of the watershed harvested, presence of buffer strips between streams and harvested areas, nature of post‐harvesting site preparation, revegetation rate following harvesting, pre‐harvesting soil fertility, and soil buffering capacity. These effects have sometimes reinforced one another but have sometimes been counterbalancing or slight so that harvesting impacts on stream water chemistry have been highly variable. Eight major knowledge gaps were identified, two of which — a scarcity of detailed stream chemical budgets and knowledge of longitudinal variation in stream chemistry — relate to undisturbed streams, while the remainder relate to forest harvesting effects.     

MODELING THE DISTRIBUTION OF DIFFUSE NITROGEN SOURCES AND SINKS IN THE NEUSE RIVER BASIN OF NORTH CAROLINA,USA1

This study quantified nonpoint source nitrogen (NPS‐N) sources and sinks across the 14,582 km² Neuse River Basin (NRB) located in North Carolina, to provide tabular data summaries and graphic overlay products to support the development of management approaches to best achieve established N reduction goals. First, a remote sensor derived, land cover classification was performed to support modeling needs. Modeling efforts included the development of a mass balance model to quantify potential N sources and sinks, followed by a precipitation event driven hydrologic model to effectively transport excess N across the landscape to individual stream reaches to support subsequent labeling of transported N values corresponding to source origin. Results indicated that agricultural land contributed 55 percent of the total annual NPS‐N loadings, followed by forested land at 23 percent (background), and urban areas at 21 percent. Average annual N source contributions were quantified for agricultural (1.4 kg/ha), urban (1.2 kg/ha), and forested cover types (0.5 kg/ha). Nonpoint source‐N contributions were greatest during the winter (40 percent), followed by spring (32 percent), summer (28 percent), and fall (0.3 percent). Seasonal total N loadings shifted from urban dominated and forest dominated sources during the winter, to agricultural sources in the spring and summer. A quantitative assessment of the significant NRB land use activities indicated that high (greater than 70 percent impervious) and medium (greater than 35 percent impervious) density urban development were the greatest contributors of NPS‐N on a unit area basis (1.9 and 1.6 kg/ha/yr, respectively), followed by row crops and pasture/hay cover types (1.4 kg/ha/yr).