Soil dissipation of sugarcane billet seed treatment fungicides and insecticide using QuEChERS and HPLC.

Chemical treatment of sugarcane seed with fungicides and insecticides prior to planting increases yields of cane and sugar for the perennial, annually harvested crop. However, the fate of the applied chemicals is unknown. Therefore, the purpose of this study was to measure the aerobic dissipation of selected billet seed treatment chemicals in a mineral sugarcane soil from Louisiana. Soil samples from the surface 15 cm were treated with either thiamethoxam, azoxystrobin, fluxapyroxad, propiconazole, or pyraclostrobin and monitored over 100 days under laboratory conditions. Insecticide and fungicide levels were determined by high performance liquid chromatography. Dissipation data were fitted to four kinetic models: simple first-order (SFO), first order multi-compartment (FOMC), double-first order in parallel (DFOP), and hockey-stick (HS). The dissipation half-life (DT50) of thiamethoxam, azoxystrobin, fluxapyroxad, propiconazole, or pyraclostrobin were 275, 100, 144, 74, and 39 d, respectively. Overall, the DT50 for the pesticides in the study indicated medium to long persistence in soil under the conditions of the experiment. This is the first report for several of these pesticides related to the aerobic dissipation in soils used to grow sugarcane.

Effect of growing media and fertilization on sugarcane flowering under artificial photoperiod.

The USDA-ARS Sugarcane Variety Development Program in Houma, LA aims to maximize the number of panicles available for crossing through artificial manipulation of the environment. In a three-year study, the effect of growing media, fertilizer treatment, and their interaction on sugarcane flowering (% of panicles emerged), and number of days to flowering (DTF) under an artificial photoperiod treatment were assessed. The commercially-available sugarcane cultivar, 'HoCP 96-540' was planted in 2.8-L pots and subjected to the standard local photoperiod treatment. The cultivar was planted in four growing media (RediEarth Seedling and Germination Mix, Fafard, Metro-Mix®902, and Metro-Mix®900) and subjected to three different fertilizer applications. In the control treatment, fertilizer application was stopped prior to the commencement of the photoperiod treatment as practiced in some sugarcane breeding programs. The continuous treatment consisted of an application of a 10 ml solution of a NPK three times a week between June and October. The partial treatment consisted of applications of the same NPK solution applied post-initiation between September and October. Nitrogen starvation prior to the commencement of the photoperiod treatment is generally accepted to improve flower initiation; thus the standard practice is to cease nitrogen application two weeks prior to beginning a photoperiod regime. The growing media used in this study did not have a significant effect on days to flowering or percent panicle emergence. In our study, the control fertilizer treatment showed a flowering percentage across all growing media types of 21.2% less than a continuous fertilization regime. Furthermore, a significant trend was observed between fertilization treatments and days to flowering, with the continuous treatment producing panicles, on average across growing media, four days earlier than the control treatment, and six days earlier than the partial treatment. Evidence across this three-year experiment indicates that we should consider modifying plant nutrition management as soil fertility was found to be inadequate.

Pyraclostrobin wash-off from sugarcane leaves and aerobic dissipation in agricultural soil.

To mitigate damage from the fungal sugarcane pathogen brown rust (Puccinia melanocephala), a Section 18 Emergency Use Label was put in place by the United States Environmental Protection Agency (U.S. EPA) for the application of pyraclostrobin (trade name Headline SC, produced by BASF, Research Triangle Park, NC) on sugarcane in 2008. To assess the dynamics of this fungicide in Louisiana soil, samples (n = 24) from a non-treated field were spiked with pyraclostrobin (3.1 µg g(-1)) and analyzed in laboratory conditions over the course of 63 days using quick, easy, cheap, effective, rugged, and safe (QuEChERS) dispersive solid-phase extraction/high-performance liquid chromatography with ultraviolet-visible detection (dSPE/HPLC-UV). Modeling was performed using Microsoft Excel to predict DTx values. Pyraclostrobin was found to follow biphasic kinetics with DT50 and DT90 values of 60 and 282 days, suggesting that it is moderately persistent to persistent in soils. Wash-off studies on sugarcane indicate that very little fungicide is in the wash-off after 48 h. If applied to sugarcane according to label recommendations, the fungicide should have minimal dissipation from rainfall events.

Metolachlor and chlorothalonil dissipation in gypsum-amended soil.

This work focused on the interactive effects of the fungicide chlorothalonil (2,3,4,6-tetrachloro-1,3-benzendicarbonitrile) and gypsum on the persistence of the soil-residual herbicide metolachlor (2-chloro-N-(6-ethyl-o-tolyl)-N-[(1RS)-2-methoxy-1-methylethyl]acetamide). Gypsum application was included due to its widespread use on peanut (Arachis hypogaea). Both agricultural grade gypsum and reagent CaSO(4)-2H(2)O were tested. A laboratory soil incubation was conducted to evaluate interactive effects. Results indicated 1.5X greater metolachlor half-life (DT(50)) in soil amended with chlorothalonil (37 d) as compared to control soil (25 d). The two gypsum sources alone increased metolachlor DT(50) to about 32 d and with the combination of chlorothalonil and gypsum, DT50 was 50 d, 2-fold greater than the control. Chlorothalonil dissipation was rapid (DT(50) < 4d). A possible explanation for metolachlor dissipation kinetics is a build-up of the chlorothalonil intermediate (4-hydroxychlorothalonil) which limited soil microbial activity and depleted glutathione S-transferase (GST) from chlorothalonil detoxification. Further information related to gypsum impacts is needed. Results confirm previous reports of chlorothalonil impeding metolachlor dissipation and showed the gypsum application extended persistence even longer. Farming practices, such as reducing metolachlor application rates, may need to be adjusted for peanut cropping systems where chlorothalonil and gypsum are used.

Fungicide dissipation and impact on metolachlor aerobic soil degradation and soil microbial dynamics.

Pesticides are typically applied as mixtures and or sequentially to soil and plants during crop production. A common scenario is herbicide application at planting followed by sequential fungicide applications post-emergence. Fungicides depending on their spectrum of activity may alter and impact soil microbial communities. Thus there is a potential to impact soil processes responsible for herbicide degradation. This may change herbicide efficacy and environmental fate characteristics. Our study objective was to determine the effects of 4 peanut fungicides, chlorothalonil (2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile), tebuconazole (alpha-[2-(4-chlorophenyl)ethyl]-alpha-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol), flutriafol (alpha-(2-fluorophenyl)-alpha-(4-fluorophenyl)-1H-1,2,4-triazole-1-ethanol), and cyproconazole (alpha-(4-chlorophenyl)-alpha-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol) on the dissipation kinetics of the herbicide, metolachlor (2-chloro-N-(6-ethyl-o-tolyl)-N-[(1RS)-2-methoxy-1-methylethyl]acetamide), and on the soil microbial community. This was done through laboratory incubation of field treated soil. Chlorothalonil significantly reduced metolachlor soil dissipation as compared to the non-treated control or soil treated with the other fungicides. Metolachlor DT(50) was 99 days for chlorothalonil-treated soil and 56, 45, 53, and 46 days for control, tebuconazole, flutriafol, and cyproconazole-treated soils, respectively. Significant reductions in predominant metolachlor metabolites, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOA), produced by oxidation of glutathione-metolachlor conjugates were also observed in chlorothalonil-treated soil. This suggested that the fungicide impacted soil glutathione-S-transferase (GST) activity. Fungicide DT(50) was 27-80 days but impacts on the soil microbial community as indicated by lipid biomarker analysis were minimal. Overall study results indicated that chlorothalonil has the potential to substantially increase soil persistence (2-fold) of metolachlor and alter fate and transport processes. GST mediated metabolism is common pesticide detoxification process in soil; thus there are implications for the fate of many active ingredients.

Reduction in metolachlor and degradate concentrations in shallow groundwater through cover crop use.

Pesticide use during crop production has the potential to adversely impact groundwater quality. In southern Florida, climatic and hydrogeologic conditions and agronomic practices indicate that contamination risks are high. In the current study, dissipation of the widely used herbicide, metolachlor, and levels of the compound and selected degradates in shallow groundwater beneath six 0.15-ha plots in sweet corn (Zea mays) production were evaluated over a two-year period. During fallow periods (May to October), plots were either left bare or cover cropped with sunn hemp (Crotalaria juncea L.). Metolachlor was broadcast applied at label recommended rates prior to planting sweet corn each year. Groundwater monitoring wells hydraulically upgradient and downgradient, and within each plot were sampled biweekly. Results showed that metolachlor dissipation was rapid, as evidenced by the detection of relatively high levels of the metolachlor ethane sulfonic degradate (MESA) in groundwater beneath plots and a rapid metolachlor DT(50) (9-14 days) in a companion laboratory soil incubation. Other degradates detected included hydroxymetolachlor in soil and in groundwater metolachlor oxanilic acid (MOA) and a product tentatively identified as 2-chloro-N-(2-acetyl-6-methylphenyl-N-(2-methoxy-1-methylethyl) acetamide, a photo-oxidation product. Metolachlor and MESA levels, up to 16 and 2.4 times higher in groundwater beneath the noncover cropped plots when compared to those of the cover cropped plots, indicate that cover cropping results in more rapid dissipation and/or reduced leaching. The study demonstrated that integration of cover crops into agronomic systems in the region may yield water quality benefits by reducing herbicide inputs to groundwater.

Pressurized liquid extraction of soil microbial phospholipid and neutral lipid fatty acids.

Soil microbial lipid biomarkers are indicators of viable microbial biomass and community structure. Pressurized liquid extraction (PLE) of soil phospholipid fatty acids (PLFA) and neutral lipid fatty acids (NLFA) was compared to a conventional extraction method in four soils with differing physical and chemical properties. PLE efficiency was greater than that of the conventional method for about half of the saturated PLFA and for selected other Gram-positive (i16:0) and Gram-negative bacteria (18:1omega7c) PLFA, fungal PLFA (18:2omega6,9c), and eukaryotic NLFA from a coarse-textured soil. Lipids extracted by the two methods did not indicate a significant difference in microbial community structure data. Principle component analysis revealed that PLFA clustered by location, with data indicating that the group of microbes contributing the greatest weight differed among soils. Overall, the PLE method proved to be more efficient at extracting soilborne microbial lipids while not altering microbial community information. These advantages indicate the PLE method is robust and well-suited to soil microbial ecology research.