Regional assessment of herbicide sorption and degradation in two sampling years

Sorption and degradation of the herbicide 2,4-D [2,4-dichlorophenoxyacetic acid] were determined for 123 surface soils (0 to 15 cm) collected in 2002 and in 2004 between 49 degrees to 60 degrees north longitude and 110 degrees to 120 degrees west latitude in Alberta, Canada. The soils were characterized by soil organic carbon content (SOC), pH, electrical conductivity, soil texture, cation exchange capacity, carbonate content, and total soil microbial activity. The 2,4-D sorption coefficients, Kd and Koc, were highly variable with coefficients of variation of 89 and 59%, respectively, at the provincial scale. Both Kd and Koc were well described by regression models with SOC and soil pH as variables, regardless of scale. Surprisingly, variations in 2,4-D mineralization were much smaller than variations in sorption. Variability in total 2,4-D mineralization was particularly low, with a coefficient of variation of only 7% at the provincial scale. Average 2,4-D half-lives in ecoregions ranged from 1.7 to 3.5 d, much lower than the field dissipation half-life of 10 d reported for 2,4-D in general pesticide property databases. Regression models describing degradation parameters were generally poor or not significant because 2,4-D mineralization was only weakly associated with measured 2,4-D sorption parameters and soil properties. As such, regional variations in herbicide sorption coefficients should be measured or calculated based on soil properties, to assign distinct pesticide fate model input parameters when estimating 2,4-D off-site transport at the provincial scale. Spatial variations in herbicide degradation appear less important for Alberta as 2,4-D half-lives were similar in soils across the province. The rapid mineralization of 2,4-D is noteworthy because 2,4-D is widely used in Alberta and perhaps adaptation of soil microbial communities allowed for accelerated degradation regardless of soil properties or the extent of 2,4-D sorption by soil.     

Soil sorption of acidic pesticides: modeling pH effects

A model of acidic pesticide sorption in soils was developed from theoretical modeling and experimental data, which initially considered a combination of a strongly acidic pesticide and a variable-charge soil with high clay content. Contribution of 2,4-D [(2,4-dichlorophenoxy) acetic acid] anionic-form sorption was small when compared with molecular sorption. Dissociation of 2,4-D was not sufficient to explain the variation in Kd as a function of pH. Accessibility of soil organic functional groups able to interact with the pesticide (conformational changes) as a function of organic matter dissociation was proposed to explain the observed differences in sorption. Experimental 2,4-D sorption data and K(oc) values from literature for flumetsulam [N-(2,6-difluorophenyl)-5-methyl [1,2,4] triazolo [1,5-a] pyrimidine-2-sulfonamide] and sulfentrazone [N-[2,4-dichloro-5-[4-(difluromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl] phenyl] methanesulfonamide] in several soils fit the model.     

Effects of soil phosphorus status on environmental risk assessment of glyphosate and glufosinate-ammonium

The increased use of herbicides poses a risk to the aquatic environment. Easy and economical methods are needed to identify the fields where specific environment protection measures are needed. Phosphorus (P) and organophosphorus herbicides compete for the same adsorption sites in soil. In this study the relationship between P obtained in routine Finnish agronomic tests (acid ammonium acetate [P(AC)]) and adsorption of glyphosate and glufosinate-ammonium was investigated to determine whether P(AC) values could be used in the risk assessment. The adsorption of glyphosate ((N-(phosphonomethyl)glycine) and glufosinate-ammonium (2-amino-4-(hydroxymethylphosphinyl)butanoic acid) was studied in a clay and a sandy loam soil enriched with increasing amounts of P added as potassium dihydrogen phosphate. Desorption was also determined for some P-enriched soil samples. The adsorption of both herbicides diminished with increasing P(AC) value. The correlations between Freundlich adsorption coefficients obtained in the adsorption tests and P(AC) were nonlinear but significant (r > 0.98) in both soils. The exponential models of the relationship between soil P(AC) values and glyphosate adsorption were found to fit well to an independent Finnish soil data set (P < 0.1 for glyphosate and P < 0.01 for glufosinate-ammonium). The desorption results showed that glufosinate-ammonium sorption is not inversely related to soil P status, and the high correlation coefficients obtained in the test of the model were thus artifacts caused by an abnormal concentration of exchangeable potassium in soil. The solved equations are a useful tool in assessing the leaching risks of glyphosate, but their use for glufosinate-ammonium is questionable.     

Aging effects on the sorption-desorption characteristics of anthropogenic organic compounds in soil

Field studies have demonstrated that prolonged pesticide-soil contact times (aging) may lead to unexpected persistence of these compounds in the environment. Although this phenomenon is well documented in the field, there have been very few controlled laboratory studies that have tested the effects of long-term aging and the role of differing sorbates on contaminant sorption-desorption behavior and fate in soils. This study examines the sorption-desorption behavior of chlorobenzene, ethylene dibromide (1,2-dibromomethane), atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), and 2, 4-D (2,4-dichlorophenoxyacetic acid) on one soil type after 1 d, 30 d, and 14 mo of aging. Sorption isotherms were evaluated after each aging period to observe changes in the uptake of each compound by soil. Desorption kinetic data were generated after each aging period to observe changes in release from soil, and desorption parameters were evaluated using a three-site desorption model that includes equilibrium, nonequilibrium, and nondesorption sites. The data indicate no statistically significant increase in sorption for ethylene dibromide or chlorobenzene from 1 to 30 d, although sorption of 2,4-D increased slightly, and sorption of atrazine decreased slightly. Statistically significant increases in linear sorption coefficients (Kd), from 1 d to 14 mo of aging, were apparent for ethylene dibromide and 2,4-D. The Kd values for chlorobenzene, measured after 1 d, 30 d, and 14 mo of aging, were statistically indistinguishable. Aging affected the distribution of chemicals within sorption sites. With aging, the desorbable fraction decreased and the nondesorbable fraction, which was apparent after only 1 d of pesticide-soil contact, increased for all chemicals studied.     

Anionic polyacrylamide effects on soil sorption and desorption of metolachlor,atrazine, 2,4-D,and picloram

Polyacrylamide (PAM) treatment of irrigation water is a growing conservation technology in irrigated agriculture in recent years. There is a concern regarding the environmental impact of PAM after its application. The effects of anionic PAM on the sorption characteristics of four widely used herbicides (metolachlor, atrazine, 2,4-D, and picloram) on two natural soils were assessed in batch equilibrium experiments. Results showed that PAM treatment kinetically reduced the sorption rate of all herbicides, possibly due to the slower diffusion of herbicide molecules into interior sorption sites of soil particles that were covered and/or cemented together by PAM. The equilibrium sorption and desorption amounts of nonionic herbicides (metolachlor and atrazine) were essentially unaffected by anionic PAM, even under a high PAM application rate, while the sorption amounts of anionic herbicides (2,4-D and picloram) were slightly decreased and their desorption amounts increased little. The impact mechanisms of PAM were related to the molecular characteristics of PAM and herbicides. The negative effects of PAM on the sorption of anionic herbicides are possibly caused by the enhancement of electrostatic repulsion by presorbed anionic PAM and competition for sorption sites. However, steric hindrance of the large PAM molecule weakens its influence on herbicide sorption on interior sorption sites of soil particles, which probably leads to the small interference on herbicide sorption, even under high application rates.     

Assessment of herbicide leaching risk in two tropical soils of Reunion Island (France)

Application of organic chemicals to a newly irrigated sugarcane (Saccharum officinarum L.) area located in the semiarid western part of Reunion Island has prompted local regulatory agencies to determine their potential to contaminate ground water resources. For that purpose, simple indices known as the ground water ubiquity score (Gustafson index, GUS), the retardation factor (RF), the attenuation factor (AF), and the log-transformed attenuation factor (AFT) were employed to assess the potential leaching of five herbicides in two soil types. The herbicides were alachlor [2-chloro-2',6'-diethyl-N-(methoxy-methy) acetanilide], atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine], diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], 2,4-D [(2,4-dichlorophenoxy) acetic-acid], and triclopyr [((3,5,6-trichloro-2-pyridyl)oxy) acetic-acid]. The soil types were Vertic (BV) and Andepts (BA) Inceptisols, which are present throughout the Saint-Gilles study area on Reunion Island. To calculate the indices, herbicide sorption (K(oc)) and dissipation (half-life, DT50) properties were determined from controlled batch experiments. Water fluxes below the root zone were estimated by a capacity-based model driven by a rainfall frequency analysis performed on a 13-yr data series. The results show a lower risk of herbicide leaching than in temperate regions due to the tropical conditions of the study area. Higher temperatures and the presence of highly adsorbent soils may explain smaller DT50 and higher K(oc) values than those reported in literature concerning temperate environments. Based on the RF values, only 2,4-D and triclopyr appear mobile in the BV soil, with all the other herbicides being classified from moderately to very immobile in both soils. The AFT values indicate that the potential leaching of the five herbicides can be considered as unlikely, except during the cyclonic period (about 40 d/yr) when there is a 2.5% probability of recharge rates equal to or higher than 50 mm/d. In that case, atrazine in both soils, 2,4-D and triclopyr in the BV soil, and diuron and alachlor in the BA soil present a high risk of potential contamination of ground water resources.     

Residual and contact herbicide transport through field lysimeters via preferential flow

Usage of glyphosate [N-(phosphonomethyl)-glycine] and glufosinate [2-amino-4-(hydroxy-methylphosphinyl)butanoic acid] may reduce the environmental impact of agriculture because they are more strongly sorbed to soil and may be less toxic than many of the residual herbicides they replace. Preferential flow complicates the picture, because due to this process, even strongly sorbed chemicals can move quickly to ground water. Therefore, four monolith lysimeters (8.1 m(2) by 2.4 m deep) were used to investigate leaching of contact and residual herbicides under a worst-case scenario. Glufosinate, atrazine (6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine), alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide], and linuron (3-3,4-dichlorophenyl-1-methoxy-1-methylurea) were applied in 1999 before corn (Zea mays L.) planting and glyphosate, alachlor, and metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] were applied in 2000 before soybean [Glycine max (L.) Merr.] planting. A high-intensity rainfall was applied shortly after herbicide application both years. Most alachlor, metribuzin, atrazine, and linuron losses occurred within 1.1 d of rainfall initiation and the peak concentration of the herbicides coincided (within 0.1 d of rainfall initiation in 2000). More of the applied metribuzin leached compared with alachlor during the first 1.1 d after rainfall initiation (2.2% vs. 0.035%, P < 0.05). In 1999, 10 of 24 discrete samples contained atrazine above the maximum contaminant level (atrazine maximum contaminant level [MCL] = 3 mug L(-1)) while only one discrete sample contained glufosinate (19 mug L(-1), estimated MCL = 150 mug L(-1)). The results indicate that because of preferential flow, the breakthrough time of herbicides was independent of their sorptive properties but the transport amount was dependent on the herbicide properties. Even with preferential flow, glyphosate and glufosinate were not transported to 2.4 m at concentrations approaching environmental concern.     

Vegetative Buffer Strips for Reducing Herbicide Transport in Runoff: Effects of Buffer Width,Vegetation, and Season

The effectiveness of vegetative buffer strips (VBS) for reducing herbicide transport has not been well documented for runoff prone soils. A multi‐year plot‐scale study was conducted on an eroded claypan soil with the following objectives: (1) assess the effects of buffer width, vegetation, and season on runoff transport of atrazine (ATR), metolachlor (MET), and glyphosate; (2) develop VBS design criteria for herbicides; and (3) compare differences in soil quality among vegetation treatments. Rainfall simulation was used to create uniform antecedent soil water content and to generate runoff. Vegetation treatment and buffer width impacted herbicide loads much more than season. Grass treatments reduced herbicide loads by 19‐28% and sediment loads by 67% compared to the control. Grass treatments increased retention of dissolved‐phase herbicides by both infiltration and adsorption, but adsorption accounted for the greatest proportion of retained herbicide load. This latter finding indicated VBS can be effective on poorly drained soils or when the source to buffer area ratio is high. Grass treatments modestly improved surface soil quality 8‐13 years after establishment, with significant increases in organic C, total N, and ATR and MET sorption compared to continuously tilled control. Herbicide loads as a function of buffer width were well described by first‐order decay models which indicated VBS can provide significant load reductions under anticipated field conditions.     

Environmental concentrations of agricultural herbicides: 2,4-d and triallate

The herbicides 2,4-D (2,4-dichlorophenoxyacetic acid) and triallate [S-2,3,3-trichloroallyl di-isopropyl(thiocarbamate)] are extensively used to control broadleaf and wild oat (respectively) weed infestations in Canadian cereal crops. In 1990, for example, more than 3.8 million kg of 2,4-D and 2.7 million kg of triallate were applied in the three prairie provinces (Alberta, Saskatchewan, and Manitoba). Maximum air concentrations of these two herbicides during the summers of 1989 and 1990 near Regina, Saskatchewan, were 3.90 ng m(-3) (2,4-D) and 60.04 ng m(-3) (triallate). Concentrations of these two herbicides were also measured in bulk atmospheric deposition (wet plus dry) and in farm pond water and associated surface film. Maximum measured levels of 2,4-D were 3550 ng m(-2) d(-1) (bulk deposition), 332 ng m(-2) (surface film), and 290 ng L(-1) (pond water). Maximum levels of triallate were 2300 ng m(-2) d(-1) (bulk deposition), 212 ng m(-2) (surface film), and 500 ng L(-1) (pond water). The highest quantities of the herbicides tended to be found during or immediately after the time of regional application. The movement of the herbicides in the environment will be discussed in relation to the four matrices studied.     

Effects of glyphosate and two herbicide mixtures on microbial communities in prairie wetland ecosystems: a mesocosm approach

A multitrophic outdoor mesocosm system was used to mimic a wetland ecosystem and to investigate the effects of glyphosate and two herbicide mixtures on wetland microbial communities. The glyphosate concentration used was 1000 times the environmentally relevant concentration (ERC). One herbicide mixture consisted of six auxin-type herbicides (2,4-D, MCPA, clopyralid, dicamba, dichlorprop, mecoprop), each at 1000 times the ERC. The second mixture was comprised of eight herbicides, including the six auxin-type herbicides as well as bromoxynil and glyphosate. For this mixture, a dose-response approach was used to treat mesocosms with the ERCs of each herbicide as the base concentration. Algal biomass and production and bacterial production and numbers for pelagic and attached communities were measured at different times over a 22-d period. The experimental results indicate that the eight-herbicide mixture, even at low concentrations, produced negative effects on microbial communities. Glyphosate on its own suppressed algal biomass and production for the duration of the study in pelagic and biofilm communities. Algal biomass and production, although initially depressed in the auxin-type herbicide treatment, were stimulated from Day 9 until experiment end. Due to their similar modes of action, the effects of this herbicide mixture appear to be a result of concentration addition. Such negative effects, however, were brief, and microbial communities recovered from herbicide exposure. Based on evidence presented in this study, it appears that glyphosate has a higher potential to inhibit primary production and chlorophyll content in pelagic and attached wetland algal communities than the auxin-type herbicide mixture.     

Picloram and napropamide sorption as affected by polymer addition and salt concentration

Polymer application to soil is a growing practice to improve soil physical properties and reduce soil erosion. Polymer addition can potentially influence herbicide and pesticide sorption in soil. The one-point distribution coefficient Kd values of two herbicides in the absence and presence of each of 10 polymers (7 polyacrylamides and 3 polysaccharides) were determined by the batch equilibrium method. The results showed that nonionic napropamide [2-(alpha-naphthoxy)-N,N-diethyl propionamide] sorption was essentially unaffected by the presence of any of the polymers. The influence of polymers on anionic picloram (4-amino-3,5,6-trichloropicolinic acid) sorption depends on the charge characteristics of polymers and salt concentrations in the solution. Electrostatic interaction and competition for sorption sites are two primary underlying mechanisms for the polymer influence. At low salt concentration, the increased picloram sorption in the presence of both cationic and anionic polymers was attributed to different electrostatic interactions and polymer partitioning between soil and solution phases. At high salt levels, the presence of polymers had either no influence or a slightly negative influence on the picloram sorption, which was attributed to competition for sorption sites. In field conditions, it is more likely that polymers have no or a slightly negative influence on herbicide sorption due to the presence of salts.     

Soil characteristics and phosphorus level effect on phosphorus loss in runoff

The loss of phosphorus (P) in runoff from agricultural soils may accelerate eutrophication in lakes and streams as well as degrade surface water quality. Limited soil specific data exist on the relationship between runoff P and soil P. This study investigated the relationship between runoff dissolved reactive phosphorus (DRP) and soil P for three Oklahoma benchmark soils: Richfield (fine, smectitic, mesic Aridic Argiustoll), Dennis (fine, mixed, active, thermic Aquic Argiudoll), and Kirkland (fine, mixed, superactive, thermic Udertic Paleustoll) series. These soils were selected to represent the most important agricultural soils in Oklahoma across three major land resource areas. Surface soil (0-15 cm) was collected from three designated locations, treated with diammonium phosphate (18-46-0) to establish a wide range of water-soluble phosphorus (WSP) (3.15-230 mg kg(-1)) and Mehlich-3 phosphorus (M3P) (27.8-925 mg kg(-1)). Amended soils were allowed to reach a steady state 210 d before simulated rainfall (75 mm h(-1)). Runoff was collected for 30 min from bare soil boxes (1.0 x 0.42 m and 5% slope) and analyzed for DRP and total P. Soil samples collected immediately before rainfall simulation were analyzed for the following: M3P, WSP, ammonium oxalate P saturation index (PSI(ox)), water-soluble phosphorus saturation index (PSI(WSP)), and phosphorus saturation index calculated from M3P and phosphorus sorption maxima (P(sat)). The DRP in runoff was highly related (p < 0.001) to M3P for individual soil series (r2 > 0.92). Highly significant relationships (p < 0.001) were found between runoff DRP and soil WSP for the individual soil series (r2 > 0.88). Highly significant relationships (p < 0.001) existed between DRP and different P saturation indexes. Significant differences (p < 0.05) among the slopes of the regressions for the DRP-M3P, DRP-WSP, DRP-PSI(ox), DRP-PSI(WSP), and DRP-P(sat) relationships indicate that the relationships are soil specific and phosphorus management decisions should consider soil characteristics.     

Small-scale spatial variability of atrazine and dinoseb adsorption parameters in an alluvial soil

Soil sorption processes largely control the environmental fate of herbicides. Therefore, accuracy of sorption parameters is crucial for accurate prediction of herbicide mobility in agricultural soils. A combined experimental and statistical study was performed to investigate the small-scale spatial variability of sorption parameters for atrazine and dinoseb in soils and to establish the number of samples needed to provide a value of the distribution coefficient (K(d)) next to the mean, with a given precision. The study explored sorption properties of the two herbicides in subsurface samples collected from four pits distributed along a transect of an alluvial soil; two to four samples were taken at about 30 cm apart at each sampling location. When considering all the data, the distribution coefficients were found to be normally and log-normally distributed for atrazine and dinoseb, respectively; the CVs were relatively high (close to 50% for dinoseb and 40% for atrazine). When analyzed horizon by horizon, the data revealed distribution coefficients normally distributed for both herbicides, whatever the soil layer, with lower CVs. The K(d) values were shown to vary considerably between samples collected at very short distance (a few centimeters), suggesting that taking a single soil sample to determine sorption properties through batch experiments can lead to highly unrepresentative results and to poor sorption/mobility predictions.     

Cadmium solubility and sorption in a long-term sludge-amended arable soil

Cadmium solubility and sorption in an arable clay loam soil that had received sewage sludge for 41 years were compared to an unsludged control in batch studies. Soil pH dominated Cd sorption, explaining >92% of the variation in Kd values in both treatments. At any pH, Cd sorption was apparently slightly but significantly (p < 0.05) smaller in the sludge-amended soil compared to the control, even though the organic carbon content was 70% larger and the ammonium oxalate-extractable iron content was roughly doubled. Correction for dissolved organic carbon (DOC) complexation with the speciation model WHAM reduced the difference in sorption between treatments, but the sludged soil still had significantly smaller Kd values (p < 0.01). Batch equilibrations without addition of Cd showed that there was no significant difference in the solubility of "native" cadmium (defined as EDTA-extractable Cd) in sludged and control soils. The reason for the lack of increase in Cd sorption in the sludge-amended soil has not been established, but it may be due to competition for sorption sites on humic compounds with sludge-derived Fe and trace metals such as zinc. The fact that the pyrophosphate-extractable (i.e., organically associated) iron content was seven times larger in the sludged soil provides some supporting evidence for this hypothesis.     

Soil organic carbon of degraded wetlands treated with freshwater in the Yellow River Delta, China

Supplying freshwater is one of the important methods to help restore degraded wetlands. Changes in soil properties and plant community biomass were evaluated by comparing sites with freshwater treatment versus reference sites following freshwater addition to wetlands of the Yellow River Delta for 7 years. The results indicated that soil organic carbon (SOC) was significantly increased in all wetland sites that were treated with freshwater compared to the reference sites. The treatment wetlands had greater total nitrogen (TN), lower pH and electrical conductivity and higher water content in the soil compared to the reference wetlands. In general, the upper soil layer (0-20 cm) had greater SOC than the lower soil layer (20-40 cm). The increase of SOC in the freshwater reintroduction wetlands was higher in the Suaeda salsa plant community (mean ± standard error) (6.89 ± 0.63 g/kg) and Phragmites communis plant community (4.11 ± 0.12 g/kg) than in the Tamarix chinensis plant community (1.40 ± 0.31 g/kg) in the upper soil layer. The differences were especially marked between the treated and reference wetlands for SOC and TN in the P. communis plant communities. The C:N ratio of the soil was significantly greater in the treated compared to the reference wetlands for the S. salsa plant community. Although the C: N ratios increased after treatment, they were all <25 suggesting that N availability was not limiting soil organic matter decomposition. Our results indicate that freshwater addition and the concomitant increase in soil moisture content enhances the accumulation of SOC in the Yellow River Delta.     

Estimating runoff phosphorus losses from calcareous soils in the Minnesota River basin

Bioavailable phosphorus (BAP) in stormwater runoff is a key issue for control of eutrophication in agriculturally impacted watersheds. Laboratory experiments were conducted in soil runoff boxes to determine BAP content in simulated storm runoff in 10 (mostly) calcareous soils from the Minnesota River basin in southern Minnesota. The soluble reactive phosphorus (SRP) portion of the runoff BAP was significantly correlated with soil Mehlich-III P, Olsen P, and water-extractable P (all r2 > 0.90 and p < 0.001). A linear relationship (r2 = 0.88, p < 0.001) also was obtained between SRP in runoff and the phosphorus saturation index based on sorptivity (PSIs) calculated with sorptivity as a measure of the inherent soil P sorption capacity. Runoff levels of BAP estimated with iron oxide-impregnated paper were predicted well by various soil test P methods and the PSI, of the soils, but correlation coefficients between these variables and runoff BAP were generally lower than those for runoff SRP. Using these relationships and critical BAP levels for stream eutrophication, we found corresponding critical levels of soil Mehlich-III P and Olsen P (which should not be exceeded) to be 65 to 85 and 40 to 55 mg kg(-1), respectively.     

Topographic Effects on Soil Organic Carbon in Louisiana Watersheds

Terrestrial carbon storage is influenced by a number of environmental factors, among which topographic and geomorphological features are of special significance. This study was designed to examine the relationships of soil organic carbon (SOC) density to various terrain parameters and watershed characteristics across Louisiana, USA. A polygon data set of 484 watersheds and 12 river drainage basins for Louisiana was used to form the landscape units. SOC densities were calculated for each soil map unit using the State Soil Geographic (STATSGO) database. Average drainage densities and average slopes at watershed and basin scales were quantified with the 1:24 K Digital Elevation Models (DEM) data, and the Louisiana hydrographic water features. Correlation and regression analyses were performed to determine relationships among drainage density, slope, elevation, and SOC. The study found an average watershed drainage density of 1.6 km/km² and an average watershed slope of 2.9 degrees in Louisiana. The results revealed that SOC density at both watershed and basin scales was closely related to drainage density, slope, and elevation. SOC density was positively correlated with watershed drainage density, but negatively correlated with watershed slope gradient and elevation. Regression models were developed for predicting SOC density at watershed and basin scales, obtaining regression coefficients (r ²) ranging from 0.43 to 0.83. The study showed that estimation of SOC at watershed and drainage basin scales combining DEM data can be a feasible approach to improve the understanding of the relationships among SOC, topographic, and geomorphological features.     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.     

Leaching of glyphosate and amino-methylphosphonic acid from Danish agricultural field sites

Pesticide leaching is an important process with respect to contamination risk to the aquatic environment. The risk of leaching was thus evaluated for glyphosate (N-phosphonomethyl-glycine) and its degradation product AMPA (amino-methylphosphonic acid) under field conditions at one sandy and two loamy sites. Over a 2-yr period, tile-drainage water, ground water, and soil water were sampled and analyzed for pesticides. At a sandy site, the strong soil sorption capacity and lack of macropores seemed to prevent leaching of both glyphosate and AMPA. At one loamy site, which received low precipitation with little intensity, the residence time within the root zone seemed sufficient to prevent leaching of glyphosate, probably due to degradation and sorption. Minor leaching of AMPA was observed at this site, although the concentration was generally low, being on the order of 0.05 microg L(-1) or less. At another loamy site, however, glyphosate and AMPA leached from the root zone into the tile drains (1 m below ground surface [BGS]) in average concentrations exceeding 0.1 microg L(-1), which is the EU threshold value for drinking water. The leaching of glyphosate was mainly governed by pronounced macropore flow occurring within the first months after application. AMPA was frequently detected more than 1.5 yr after application, thus indicating a minor release and limited degradation capacity within the soil. Leaching has so far been confined to the depth of the tile drains, and the pesticides have rarely been detected in monitoring screens located at lower depths. This study suggests that as both glyphosate and AMPA can leach through structured soils, they thereby pose a potential risk to the aquatic environment.     

Phosphorus leaching in relation to soil type and soil phosphorus content

Phosphorus losses from arable soils contribute to eutrophication of freshwater systems. In addition to losses through surface runoff, leaching has lately gained increased attention as an important P transport pathway. Increased P levels in arable soils have highlighted the necessity of establishing a relationship between actual P leaching and soil P levels. In this study, we measured leaching of total phosphorus (TP) and dissolved reactive phosphorus (DRP) during three years in undisturbed soil columns of five soils. The soils were collected at sites, established between 1957 and 1966, included in a long-term Swedish fertility experiment with four P fertilization levels at each site. Total P losses varied between 0.03 and 1.09 kg ha(-1) yr(-1), but no general correlation could be found between P concentrations and soil test P (Olsen P and phosphorus content in ammonium lactate extract [P-AL]) or P sorption indices (single-point phosphorus sorption index [PSI] and P sorption saturation) of the topsoil. Instead, water transport mechanism through the soil and subsoil properties seemed to be more important for P leaching than soil test P value in the topsoil. In one soil, where preferential flow was the dominant water transport pathway, water and P bypassed the high sorption capacity of the subsoil, resulting in high losses. On the other hand, P leaching from some soils was low in spite of high P applications due to high P sorption capacity in the subsoil. Therefore, site-specific factors may serve as indicators for P leaching losses, but a single, general indicator for all soil types was not found in this study.