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.     

Mycorrhizae increase arsenic uptake by the hyperaccumulator Chinese brake fern (Pteris vittata L.)

Chinese brake fern (Pteris vittata L.) is a hyperaccumulator of arsenic (As) that grows naturally on soils in the southern United States. It is reasonable to expect that mycorrhizal symbiosis may be involved in As uptake by this fern. This is because arbuscular mycorrhizal (AM) fungi have a well-documented role in increasing plant phosphorus (P) uptake, P and As have similar chemical properties, and ferns are known to be colonized by AM fungi. We conducted a factorial greenhouse experiment with three levels of As (0, 50, and 100 mg kg(-1)) and P (0, 25, and 50 mg kg(-1)) and with and without Chinese brake fern colonized by a community of AM fungi from an As-contaminated site. We found that the AM fungi not only tolerated As amendment, but their presence increased frond dry mass at the highest As application rate. Furthermore, the AM fungi increased As uptake across a range of P levels, while P uptake was generally increased only when there was no As amendment. These data indicate that AM fungi have an important role in arsenic accumulation by Chinese brake fern. Therefore, to effectively phytoremediate As-contaminated soils, the mycorrhizal status of ferns needs to be taken into account.     

An alum-based water treatment residual can reduce extractable phosphorus concentrations in three phosphorus-enriched coastal plain soils

The accumulation of excess soil phosphorus (P) in watersheds under intensive animal production has been linked to increases in dissolved P concentrations in rivers and streams draining these watersheds. Reductions in water dissolved P concentrations through very strong P sorption reactions may be obtainable after land application of alum-based drinking water treatment residuals (WTRs). Our objectives were to (i) evaluate the ability of an alum-based WTR to reduce Mehlich-3 phosphorus (M3P) and water-soluble phosphorus (WSP) concentrations in three P-enriched Coastal Plain soils, (ii) estimate WTR application rates necessary to lower soil M3P levels to a target 150 mg kg(-1) soil M3P concentration threshold level, and (iii) determine the effects on soil pH and electrical conductivity (EC). Three soils containing elevated M3P (145-371 mg kg(-1)) and WSP (12.3-23.5 mg kg(-1)) concentrations were laboratory incubated with between 0 and 6% WTR (w w(-1)) for 84 d. Incorporation of WTR into the three soils caused a near linear and significant reduction in soil M3P and WSP concentrations. In two soils, 6% WTR application caused a soil M3P concentration decrease to below the soil P threshold level. An additional incubation on the third soil using higher WTR to soil treatments (10-15%) was required to reduce the mean soil M3P concentration to 178 mg kg(-1). After incubation, most treatments had less than a half pH unit decline and a slight increase in soil EC values suggesting a minimal impact on soil quality properties. The results showed that WTR incorporation into soils with high P concentrations caused larger relative reductions in extractable WSP than M3P concentrations. The larger relative reductions in the extractable WSP fraction suggest that WTR can be more effective at reducing potential runoff P losses than usage as an amendment to lower M3P concentrations.     

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.     

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.     

The acetochlor registration partnership surface water monitoring program for four corn herbicides

A surface drinking water monitoring program for four corn (Zea mays L.) herbicides was conducted during 1995-2001. Stratified random sampling was used to select 175 community water systems (CWSs) within a 12-state area, with an emphasis on the most vulnerable sites, based on corn intensity and watershed size. Finished drinking water was monitored at all sites, and raw water was monitored at many sites using activated carbon, which was shown capable of removing herbicides and their degradates from drinking water. Samples were collected biweekly from mid-March through the end of August, and twice during the off-season. The analytical method had a detection limit of 0.05 microg L(-1) for alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)-acetamide] and 0.03 microg L(-1) for acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide], atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine], and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide]. Of the 16528 drinking water samples analyzed, acetochlor, alachlor, atrazine, and metolachlor were detected in 19, 7, 87, and 53% of the samples, respectively. During 1999-2001, samples were also analyzed for the presence of six major degradates of the chloroacetanilide herbicides, which were detected more frequently than their parent compounds, despite having higher detection limits of 0.1 to 0.2 microg L(-1). Overall detection frequencies were correlated with product use and environmental fate characteristics. Reservoirs were particularly vulnerable to atrazine, which exceeded its 3 microg L(-1) maximum contaminant level at 25 such sites during 1995-1999. Acetochlor annualized mean concentrations (AMCs) did not exceed its mitigation trigger (2 microg L(-1)) at any site, and comparisons of observed levels with standard measures of human and ecological hazards indicate that it poses no significant risk to human health or the environment.