Danielle P. Oliver

Faster degradation of herbicidally-active enantiomer of imidazolinones in soils

Imidazolinones are chiral herbicides, comprised of two enantiomers with differential herbicidal activity. In this study, the selective degradation of enantiomers of the three imidazolinone herbicides, imazapyr, imazethapyr and imazaquin, was determined in a variety of soils selected to cover a broad range of physico-chemical characteristics. The R(+) enantiomer of all three herbicides, which has greater herbicidal activity (up to eight times), was found to degrade faster than the less active S(-) enantiomer. The enantiomer fraction (EF) was used as a descriptor of enantio-selectivity of the imidazolinone herbicides. The EF values increased with increasing incubation time for imidazolinones with a fast initial phase followed by a slower phase. While the enantio-selectivity was not significant in acidic soils (pH(w) 5.02 and 5.20), it was highly significant (P<0.001) in alkaline soils (pH(w) 7.6, 8.2 and 8.7). Significant positive correlations of EF values of imazapyr (P<0.001, R(2)=0.41), imazethapyr (P<0.002, R(2)=0.47) and imazaquin (P<0.001, R(2)=0.54) were found with the soil pH(w) ranging from 5.02 to 8.7. However, no correlation of EF was found with other soil properties. In addition to showing enantioselective degradation of the three herbicides in the soils studied, the study highlighted that for imidazolinones the herbicidally more active enantiomer can be preferably degraded by microorganisms.

Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.

Improved extraction and clean-up of imidazolinone herbicides from soil solutions using different solid-phase sorbents ☆

Extraction and quantification of herbicide residues from soil are important in understanding the behaviour of persistent herbicides. This research investigated extraction and clean-up methods for imidazolinone herbicides from soil and soil amended with organic material. A series of solvent mixes, pH conditions and sorbents was tested. Across three imidazolinone herbicides: imazapyr, imazethapyr and imazaquin, 0.5M NaOH extraction gave greater than 90% recovery from soil samples; however, 0.5M NaOH:MeOH (80:20) resulted in higher recovery for imazaquin, but not for the other two herbicides. Of the sorbents tested, the use of chromatographic mode sequencing using C(18) and SCX sorbents provided consistent high (>85%) recovery of all three herbicides from soil and separation of the herbicides from other soil components by high performance liquid chromatography (HPLC). These two methods will allow high recovery of these imidazolinone herbicides from soil and have the ability to detect these herbicides without interference from other soil components.

Minimising off-site movement of contaminants in furrow irrigation using polyacrylamide (PAM). I. Pesticides

Off-site movement of pesticides from furrow-irrigated agriculture has been a concern in the Ord River Irrigation Area, Western Australia. After consultation with growers a range of management strategies were tested to assess the effectiveness of various practices to minimise off-site movement of pesticides during irrigation. This paper reports on the effectiveness of the additions of high molecular weight, anionic, polyacrylamide (PAM) to irrigation water to minimise off-site movement of endosulfan, chlorothalonil, bupirimate, and atrazine. Water leaving from 4 separate irrigation bays, which consisted of 25 furrows per irrigation bay (Expt 1) or 39 furrows per irrigation bay (Expt 2), was monitored over time. The average concentration of endosulfan α and β and bupirimate leaving the irrigation bays for the duration of the single irrigation event was generally always less for the PAM-treated irrigation bays than the control (control treatment). The addition of PAM to the irrigation water significantly decreased the cumulative runoff losses (g) of total endosulfan by 54% from 11.41 to 5.19 g/ha (P < 0.05), and of chlorothalonil by 49% from 53.65 to 27.32 g/ha (P < 0.001). There was no statistical difference in the load of atrazine or bupirimate leaving either treatment. Although the addition of PAM to irrigation water effectively decreased the off-site movement of 2 fairly strongly sorbed pesticides, endosulfan and chlorothalonil, it did not decrease the total load moving off-site of the more weakly sorbed pesticides, bupirimate and atrazine. The addition of PAM as a liquid to irrigation water was not found to increase the infiltration of a soluble pesticide, atrazine, into the soil profile. The mode of application of PAM, however, may affect water infiltration and hence vertical movement of soluble pesticides and requires further investigation.

Banded applications are highly effective in minimising herbicide migration from furrow-irrigated sugar cane

Runoff from farm fields is a common source of herbicide residues in surface waters in many agricultural industries around the world. In Queensland, Australia, the runoff of PSII inhibitor herbicides (in particular diuron and atrazine) is a major concern due to their potential impact on the Great Barrier Reef. This study compared the conventional practice of broadcast application of herbicides in sugarcane production across the whole field with the banded application of particular herbicides onto raised beds only using a shielded sprayer. This study found that the application of two moderately soluble herbicides, diuron and atrazine, to only the raised beds decreased the average total load of both herbicides moving off-site by >90% compared with the conventional treatment. This was despite the area being covered with the herbicides by the banded application being only 60% less than with the conventional treatment. The average total amount of atrazine in drainage water was 7.5% of the active ingredient applied in the conventional treatment compared with 1.8% of the active ingredient applied in the banded application treatment. Similarly, the average total amount of diuron in drainage water was 4.6% of that applied in the conventional treatment compared with 0.9% of that applied in the banded application treatment. This study demonstrates that the application of diuron and atrazine to raised beds only is a highly effective way of minimising migration of these herbicides in drainage water from furrow irrigated sugarcane.

Land use effects on sorption of pesticides and their metabolites in sandy soils. II. Atrazine and two metabolites, deethylatrazine and deisopropylatrazine, and prometryne

There is very limited information about the effect of land use on sorption behaviour of organic chemicals. The effects of land use on the sorption behaviour of prometryne, atrazine, and its 2 main metabolites, deethylatrazine (DEA) and deisopropylatrazine (DIA), in sandy soils were studied. This study would provide fate data for these chemicals specifically for Australian soils. Sorption coefficients (Kd) were determined using batch studies and a single solution concentration (2 mg/L for atrazine, DEA, and DIA, and 3 mg/L for prometryne) after initially determining sorption isotherms for a subset of 6 soils for atrazine and prometryne using a range of concentrations. Generally, the Kd values for prometryne were significantly (P 5, but at more acidic pH values the data deviated from the model predictions suggesting an increase in the cationic form of the pesticide that readily bind to negatively charged clay particles rather than OC. This study demonstrated that land use significantly (P < 0.05) affected the sorption behaviour of DIA, atrazine, and prometryne. It also highlighted the potential risk that pesticide metabolites may pose in areas where groundwater is used as a drinking water supply. Clearly there is a need for the metabolites to be considered when establishing guidelines for drinking water.

Land use effects on sorption of pesticides and their metabolites in sandy soils. I. Fenamiphos and two metabolites, fenamiphos sulfoxide and fenamiphos sulfone, and fenarimol and azinphos methyl

There is very limited information about the effect of land use on sorption behaviour of organic chemicals. It has been documented that clearing natural vegetation and cropping soil typically decreases the original organic carbon (OC) content of soil. Because OC is one of the major parameters controlling pesticide sorption, the effects of land use on the sorption behaviour of fenamiphos and its 2 main metabolites, fenamiphos sulfone (f. sulfone) and fenamiphos sulfoxide (f. sulfoxide), together with fenarimol and azinphos methyl were investigated. Based on sorption isotherms for a subset of soils, using a range of concentrations (2.5, 5.0, 7.5, and 10 mg/L), the use of a single concentration (2 mg/L) was considered adequate to determine sorption coefficients. Generally the Kd values for fenamiphos were significantly (P > f. sulfone ≥ f. sulfoxide. As both metabolites can apparently move more easily through soil than fenamiphos, they would pose a greater risk to groundwater contamination. For all compounds, only weak relationships were determined between Kd and pH or %silt + clay. Similarly, the relationship between Kd and %OC was poor, when data from all soils were combined for analysis. However, a strong relationship was obtained between sorption coefficients and %OC for fenamiphos in market garden soils (r 2 = 0.76***). This was also the case for azinphos methyl and fenarimol, particularly in soils under native vegetation (r 2 = 0.71 and 0.73***, respectively). At a given OC content, the soils under Banksia bush generally showed greater sorption than those under market gardens. This effect became more pronounced with increasing OC content, suggesting that the nature and composition of the OC in soils under native vegetation are likely to be different from that in cultivated soils. Clearly the OC content is not an adequate parameter describing the complex interactions between pesticides and organic matter. SR fe r st oi D. P ver et Additional keywords: sorption coefficients, Koc, land use, uncultivated soils, Kd.

A critical analysis of published data to discern the role of soil and sediment properties in determining sorption of per and polyfluoroalkyl substances (PFASs)

Widespread usage of per- and polyfluoroalkyl substances (PFASs) has caused major environmental contamination globally. The hydrophilic and hydrophobic properties of PFASs affect the sorption behaviour and suggest organic carbon may not be the only factor affecting sorption. We reviewed the quality of all data published in peer-reviewed literature on sorption of PFASs to critically evaluate the role organic carbon (OC) and other properties have in sorption of PFASs in soils or sediments. The largest data sets available were for perfluorooctanoic acid (PFOA, n = 147) and perfluorooctane sulfonic acid (PFOS, n = 178), and these analyses showed very weak correlations between sorption coefficient (Kd) and OC alone (R2 = 0.05-0.07). When only laboratory-derived Kd values of PFASs and OC were analysed, the R2 values increased for PFOA (R2 = 0.24, n = 42), PFOS (R2 = 0.38, n = 69), perfluorononanoic acid (PFNA, R2 = 0.77 n = 12), and perfluorodecanoic acid (PFDA, R2 = 0.78, n = 13). However, the relationships were heavily skewed by one or two high OC values. Similarly there was no significant relationship between Kd values and pH for PFOS (R2 = 0.06) and PFOA (R2 = 0.07), across a range of environmental pH values. Our analyses showed sorption behaviour of a range of PFASs could not be explained by a single soil or sediment property. Multiple regression models better explained the sorption behaviour of a number of PFASs. Regressions of OC and pH together explained a significant proportion of the variation in Kd values for 9 out of 14 PFASs and 8 of these regressions had ≥10 data points. This review highlighted that at least OC, pH and clay content are properties having significant effect on sorption. There is a clear need for more data and studies with thorough characterisation of soils or sediments to better understand their role in PFASs sorption. Current assessments based on OC alone are likely to be erroneous.

Comparative environmental impact assessment of herbicides used on genetically modified and non-genetically modified herbicide-tolerant canola crops using two risk indicators

Canola (Brassica napus L.) is the third largest field crop in Australia by area sown. Genetically modified (GM) and non-GM canola varieties released or being developed in Australia include Clearfield® (imidazolinone tolerant), TT (triazine tolerant), InVigor® (glufosinate-ammonium tolerant), Roundup Ready® - RR® (glyphosate tolerant) and Hyola® RT® (tolerant to both glyphosate and triazine). We used two risk assessment approaches - the Environmental Impact Quotient (EIQ) and the Pesticide Impact Rating Index (PIRI) - to compare the environmental risks associated with herbicides used in the canola varieties (GM and non-GM) that are currently grown or may be grown in the future. Risk assessments found that from an environmental impact viewpoint a number of herbicides used in the production of TT canola showed high relative risk in terms of mobility and ecotoxicity of herbicides. The EIQ field use rating values for atrazine and simazine in particular were high compared with those for glyphosate and trifluralin. Imazapic and imazapyr, which are only used in Clearfield® canola, had extremely low EIQ field use rating values, likely reflecting the very low application rates used for these chemicals (0.02 to 0.04kg/ha) compared with those used for atrazine and simazine (1.2 to 1.5kg/ha). The PIRI assessment showed that irrespective of the canola variety grown, trifluralin posed a high toxicity risk to fish (Rainbow trout, Oncorhynchus mykiss), algae and Daphnia sp. While the replacement of trifluralin with propyzamide had little effect on the mobility score, it greatly decreased the ecotoxicity score to fish, algae and Daphnia sp. due to the lower LC50 values for propyzamide compared with trifluralin. This study has shown that based on likelihood of off-site transport of herbicides in surface water and potential toxicity to non-target organisms, the GM canola varieties have no advantage over non-herbicide tolerant (non HT) or Clearfield® canola.

Sorption of pesticides by a mineral sand mining by-product, neutralised used acid (NUA)

This study investigated the sorption-desorption behaviour of four pesticides by a by-product from mineral sand mining, commonly referred to as neutralised used acid (NUA). In batch studies the average amount of pesticide removed after 6h was 69% for atrazine, 89% for diuron, 61% for 2,4-D and 83% for chlorpyrifos. The lower sorption of 2,4-D to NUA compared with the other pesticides studied is most likely to be due to the high pH of the solutions (7.8 to 8.8) which would have resulted in 2,4-D being predominantly in an anionic form. The presence of other pesticides only significantly decreased the amount of 2,4-D sorbed from 59% to 34% when present in a mixture. Little (2 to 17%) diuron, chlorpyrifos, atrazine or 2,4-D were found to desorb from the NUA. The presence of nitrate or phosphate had minimal effect on the amount of diuron or atrazine sorbed to the NUA. However, all phosphate and nitrate treatments significantly (P<0.05) decreased the amount of 2,4-D sorbed (<50%) compared with when 2,4-D was present alone (65%). This study has shown that NUA has potential to be used as a sorbent for pesticides.