Polynomial response of 2,4-D mineralization to temperature in soils at varying soil moisture contents,slope positions and depths

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is a widely used broadleaf control agent in cereal production systems. Although 2,4-D soil-residual activity (half-lives) are typicaly less than 10 days, this herbicide also has as a short-term leaching potential due to its relatively weak retention by soil constituents. Herbicide residual effects and leaching are influenced by environmental variables such as soil moisture and temperature. The objective of this study was to determine impacts of these environmental variables on the magnitude and extent of 2,4-D mineralization in a cultivated undulating Manitoba prairie landscape. Microcosm incubation experiments were utilized to assess 2,4-D half-lives and total mineralization using a 4 × 4 × 3 × 2 factorial design (with soil temperature at 4 levels: 5, 10, 20 and 40°C; soil moisture at 4 levels: 60, 85, 110, 135 % of field capacity; slope position at 3 levels: upper-, mid- and lower-slopes; and soil depth at 2 levels: 0–5 cm and 5–15 cm). Half-lives (t_1/2) varied from 3 days to 51 days with the total 2,4-D mineralization (M _T ) ranging from 5.8 to 50.9 %. The four-way interaction (temperature × moisture × slope × depth) significantly (p< 0.001) influenced both t_1/2 and M _T. Second-order polynomial equations best described the relations of temperature with t_1/2 and M_T as was expected from a biological system. However, the interaction and variability of t_1/2 and M_T among different temperatures, soil moistures, slope positions, and soil depth combinations indicates that the complex nature of these interacting factors should be considered when applying 2,4-D in agricultural fields and in utilizing these parameters in pesticide fate models.     

Modelling soil carbon development in Swedish coniferous forest soils—An uncertainty analysis of parameters and model estimates using the GLUE method

Boreal forest soils such as those in Sweden contain a large active carbon stock. Hence, a relatively small change in this stock can have a major impact on the Swedish national CO₂ balance. Understanding of the uncertainties in the estimations of soil carbon pools is critical for accurately assessing changes in carbon stocks in the national reports to UNFCCC and the Kyoto Protocol. Our objective was to analyse the parameter uncertainties of simulated estimates of the soil organic carbon (SOC) development between 1994 and 2002 in Swedish coniferous forests with the Q model. Both the sensitivity of model parameters and the uncertainties in simulations were assessed. Data of forests with Norway spruce, Scots pine and Lodgepole pine, from the Swedish Forest Soil Inventory (SFSI) were used. Data of 12 Swedish counties were used to calibrate parameter settings; and data from another 11 counties to validate. The “limits of acceptability” within GLUE were set at the 95% confidence interval for the annual, mean measured SOC at county scale. The calibration procedure reduced the parameter uncertainties and reshaped the distributions of the parameters county-specific. The average measured and simulated SOC amounts varied from 60 t C ha⁻¹ in northern to 140 t C ha⁻¹ in the southern Sweden. The calibrated model simulated the soil carbon pool within the limits of acceptability for all calibration counties except for one county during one year. The efficiency of the calibrated model varied strongly; for five out of 12 counties the model estimates agreed well with measurements, for two counties agreement was moderate and for five counties the agreement was poor. The lack of agreement can be explained with the high inter-annual variability of the down-scaled measured SOC estimates and changes in forest areas over time. We conclude that, although we succeed in reducing the uncertainty in the model estimates, calibrating of a regional scale process-oriented model using a national scale dataset is a sensitive balance between introducing and reducing uncertainties. Parameter distributions showed to be scale sensitive and county specific. Further analysis of uncertainties in the methods used for reporting SOC changes to the UNFCCC and Kyoto protocol is recommended.     

The effect of propanil co-application on 2,4-D sorption by soil

The herbicide 2,4-D is often applied as a tank mixture in combination with other herbicide products. However, current information on 2,4-D sorption by soil is largely based on batch-equilibrium experiments without considering the competition of other herbicides for sorption sites by soil. This study quantified the effect of the herbicide propanil on the sorption of 2,4-D in soil. Results indicated that propanil competed with 2,4-D for sorption sites, particularly in soils with an organic carbon content greater than 3.6%. The decrease in 2,4-D sorption by soil, as a result of propanil competition, was most notably for herbicide concentrations that are typical of recommended field rates. We conclude that herbicide co-applications on agricultural fields have the potential to increase the mobility of herbicides in soil.     

Solid beef cattle manure application impacts on soil properties and 17β-estradiol fate in a clay loam soil

Livestock manure applied to agricultural land is one of the ways natural steroid estrogens enter soils. To examine the impact of long-term solid beef cattle (Bos Taurus) manure on soil properties and 17β-estradiol sorption and mineralization, this study utilized a soil that had received beef cattle manure over 35 years. The 17β-estradiol was strongly sorbed and sorption significantly increased (P < 0.05) with increasing soil organic carbon content (SOC) and with an increasing annual rate of beef cattle manure. The 17β-estradiol mineralization half-life was significantly negatively correlated, and the total amount of 17β-estradiol mineralized at 90 days (MAX) was significantly positively correlated with 17β-estradiol sorption. The long-term rate of manure application had no significant effect on MAX, but the addition of fresh beef cattle manure in the laboratory resulted in significantly (P < 0.05) smaller MAX values. None of the treatments showed MAX values exceeding one-third of the 17β-estradiol applied.     

Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.     

Atrazine sorption by hydroxy-interlayered clays and their organic complexes

This study examined the sorption of atrazine by hydroxy-Fe interlayered montmorillonite (FeMt) and its hydroquinone (FeMtHQ), citrate (FeMtCt) and catechol (FeMtCC) complexes as well as by hydroxy-Al interlayered montmorillonite (AlMt) and its hydroquinone (AlMtHQ) and citrate (AlMtCt) complexes. Found among the clays were sorption distribution coefficients (K(d)) ranging from 24 to 123 mL g(-1) and maximum sorption (M) ranging from 2.2 to 16.8 microg g(-1). Both K(d) and M decreased in the order of FeMtCC > FeMtHQ > AlMtHQ > (AlMt = FeMt) > (AlMtCt = FeMtCt). The pH was negatively correlated with both K(d) (r = -0.90, p < 0.001) and M (r = -0.81, p < 0.001). When interlayered clays were associated with humified material (FeMtCC, FeMtHQ, AlMtHQ), both K(d) (r > 0.96, p < 0.01) and M (r > 0.94, p < 0.01) were highly positively correlated with total organic C and alkali-soluble C. However, clays with non-humified organic compounds (FeMtCt and AlMtCt) sorbed less atrazine than clays without any organic C (FeMt and AlMt). This suggests that functional groups of Fe-OH and Al-OH in FeMt and AlMt reduced the available sorption sites for atrazine by making complexes with citrate ions while forming FeMtCt and AlMtCt. The atrazine was sorbed through the hydrophobic interactions with organic compound surfaces as well as through H-bonding and ionic bonding with clay-mineral surfaces.     

Herbicide sorption coefficients in relation to soil properties and terrain attributes on a cultivated prairie

The sorption of 2,4-D and glyphosate herbicides in soil was quantified for 287 surface soils (0-15 cm) collected in a 10 x 10 m grid across a heavily eroded, undulating, calcareous prairie landscape. Other variables that were determined included soil carbonate content, soil pH, soil organic carbon content (SOC), soil texture, soil loss or gain by tillage and water erosion, and selected terrain attributes and landform segments. The 2,4-D sorption coefficient (Kd) was significantly associated with soil carbonate content (-0.66; P < 0.001), soil pH (-0.63; P < 0.001), and SOC (0.47; P < 0.001). Upper slopes were strongly eroded and thus had a significantly greater soil carbonate content and less SOC compared with lower slopes that were in soil accumulation zones. The 2,4-D Kd was almost twice as small in upper slopes than in lower slopes. The 2,4-D Kd was also significantly associated with nine terrain attributes, particularly with compounded topographic index (0.59; P < 0.001), gradient (-0.48; P < 0.001), mean curvature (-0.43; P < 0.001), and plan curvature (-0.42 P < 0.001). Regression equations were generated to estimate herbicide sorption in soils. The predicted power of these equations increased for 2,4-D when selected terrain attributes were combined with soil properties. In contrast, the variation of glyphosate sorption across the field was much less dependent on our measured soil properties and calculated terrain attributes. We conclude that the integration of terrain attributes or landform segments in pesticide fate modeling is more advantageous for herbicides such as 2,4-D, whose sorption to soil is weak and influenced by subtle changes in soil properties, than for herbicides such as glyphosate that are strongly bound to soil regardless of soil properties.     

Sorption and desorption of three endocrine disrupters in soils

Sorption of the estrogens estrone (E1), 17beta-estradiol (E2) and 17alpha-ethynylestradiol (EE2) on four soils was examined using batch equilibrium experiments with initial estrogen concentrations ranging from 10 to 1000 ng mL-1. At all concentrations, >85% of the three estrogens sorbed rapidly to a sandy soil. E1 sorbed more strongly to soil than E2 or EE2. Partial oxidation of E2 to E1 was observed in the presence of soils. Autoclaving was more effective at reducing this conversion than inhibition with sodium azide or mercuric chloride, and had little effect on sorption, relative to the chemical microbial inhibitors. Sorption of EE2 was greater for fine-textured than coarse-textured soils, but greater than 90% of EE2 sorbed onto all four soils. The greatest degree of desorption of estrogens from the sandy soil occurred with the lowest initial concentration of 10 ng mL-1 and reached levels >or=80% for E1 and E2. Desorption of EE2 was greater in coarser textured soils than finer-textured soils. Again, relative desorption from all soils was greatest with low initial concentrations. Therefore, at environmentally relevant concentrations, estrogens quickly sorb to soils, and soils have a large capacity to bind estrogens, but these endocrine-disrupting compounds can become easily desorbed and released into the aqueous phase.     

Factors influencing 2,4-D sorption and mineralization in soil

This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2.4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 microg(1 - 1/n) g(-1) mL(1/n). First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.