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Sorption of non-ionic organic compounds to soil is usually expressed as the carbon-normalized partition coefficient (KOC), because it is assumed that the main factor that influences the amount sorbed is the organic carbon content of the soil. However, KOC can vary by a factor of at least ten across a range of soils. We investigated two potential causes of variation in diuron KOC - organic matter-mineral interactions and organic matter chemistry - for a diverse set of 34 soils from Sri Lanka, representing a wide range of soil types. Treatment with hydrofluoric acid (HF-treatment) was used to concentrate soil organic matter. HF-treatment increased KOC for the majority of soils (average factor 2.4). We attribute this increase to the blocking of organic matter sorption sites in the whole soils by minerals. There was no significant correlation between KOC for the whole soils and KOC for the HF-treated soils, indicating that the importance of organic matter-mineral interactions varied greatly amongst these soils. There was as much variation in KOC across the HF-treated soils as there was across the whole soils, indicating that the nature of soil organic matter is also an important contributor to KOC variability. Organic matter chemistry, determined by solid-state (13)C nuclear magnetic resonance (NMR) spectroscopy, was correlated with KOC for the HF-treated soils. In particular, KOC increased with the aromatic C content (R=0.64, p=1×10(-6)), and decreased with O-alkyl C (R=-0.32, p=0.03) and alkyl C (R=-0.41, p=0.004) content., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

We studied the sorption-desorption behaviour of two herbicides (diuron and artrazine) in a soil rich in Fe and Al oxides (Ferrosol), either amended freshly with two different types of biochars or that contained biochars aged under field conditions. Standard batch sorption-desorption experiments were conducted on soil samples freshly amended with two biochars, (namely, poultry litter - PL and paper mill - PM sludge) as well on those collected from field 32 months after biochar application. Soils that were freshly amended with biochars @ 10 t ha(-1) showed a two (PM) to five (PL) fold increase in sorption of herbicides as compared with that in the unamended soil. For example, the fresh amendments with PL biochar at 10 t ha(-1) led to a highly significant (P<0.001) increase in the Freundlich sorption coefficient (K(f)) of atrazine; i.e. 20.71 (n=0.40) as compared with 4.02 (n=0.70) for the control soil. Sorption was reversible in the unamended soil but sorption-desorption hysteresis was prominent in the soil amended with fresh biochars. In contrast, the soil containing aged biochars (at 10 t ha(-1)) exhibited sorption-desorption properties that were statistically similar to that of the control soil, especially for atrazine. Ageing of biochars in the soil over a 32 months period reduced the sorption capacity by 47% (PM) to 68% (PL) for diuron. These findings may have implications for herbicide efficacy in biochar amended soils., (Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.)

We investigated how the sorption affinity of diuron (3'-(3,4-dichlorophenyl)-1,1-dimenthyl-urea), a moderately hydrophobic herbicide, is affected by soil properties, topography and management practices in an intensively managed orchard system. Soil-landscape analysis was carried out in an apple orchard which had a strong texture contrast soil and a landform with relief difference of 50 m. Diuron sorption (K(d)) affinity was successfully predicted (R(2)=0.79; p<0.001) using a mid-infrared - partial least squares model and calibrated against measured data using a conventional batch sorption technique. Soil and terrain properties explained 75% of the variance of diuron K(d) with TOC, pH(w), slope and WI as key variables. Mean diuron K(d) values were also significantly different (p<0.05) between alley and tree line and between the different management zones. Soil in the tree line generally had lower sorption capacity for diuron than soil in the alleys. Younger stands, which were found to have lower TOC than in the older stands, also had lower diuron K(d) values. In intensively managed orchards, sorption affinity of pesticides to soils was not only affected by soil properties and terrain attributes but also by management regime., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The effect of solvent-conditioning on the sorption of diuron and phenanthrene was investigated. The organic carbon-normalized sorption coefficients (K(OC)) for diuron and phenanthrene (determined from single initial concentrations of 0.8mgL(-1) and 1.5mgL(-1), respectively) were consistently higher following solvent-conditioning of a whole soil with five organic solvents (acetonitrile, acetone, methanol, chloroform and dichloromethane). The relative increase in K(OC) was inversely related to the polarity of the conditioning solvent (i.e. greater increases in K(OC) were observed for the least polar solvents: chloroform and dichloromethane). The effect of solvent-conditioning on the sorption properties of the same soil that had been lipid-extracted using accelerated solvent extraction (ASE) was also investigated. Since lipid extraction involves treatment with a non-polar solvent (95:5 dichloromethane:methanol) one may have expected no further increase in K(OC) on solvent-conditioning. On the contrary, the lipid-extracted soil exhibited very similar increases in K(OC) as the whole soil. This demonstrated that lipid removal and solvent-conditioning, which both increased K(OC) for this soil, are quite separate phenomena.

Both visible near-infrared (VNIR) and mid-infrared (MIR) spectroscopy have been claimed to better predict pesticide sorption in soils than other methods. We compared the performances of VNIR and MIR spectroscopy for predicting both organic carbon content (foc) and the sorption affinity (Kd) of diuron in 112 surface soils from South Australia. Separate calibration models were developed between VNIR and MIR spectra, and foc and Kd using partial least-squares (PLS) regression. MIR clearly outperformed VNIR for predictions of both foc and Kd in soils. Correlation (R2) and accuracy (RPD) indices were 0.4 and 1.3 for the VNIR-PLS model versus 0.8 and 2.3 for the MIR-PLS model, respectively, for Kd prediction. PLS loadings for sorption prediction were compared in terms of the soil information they contained. While VNIR loading did not include any direct spectral information regarding soil minerals, MIR loading included peaks associated with sand, clays, and carbonates. Perhaps by better predicting foc and integrating the effects of OC as well as minerals, the MIR-PLS model provided a better prediction for diuron Kd values in our calibration set.

The influence of lipids on the sorption of diuron and phenanthrene to soils was investigated. Accelerated solvent extraction (ASE) was used to extract lipids from twelve soil horizons. Extractable lipids accounted for 3-13% of organic C. The organic carbon-normalized sorption coefficients (K(OC)) for diuron and phenanthrene were consistently higher for the lipid-extracted soils than for the whole soils (average of 31% for diuron and 29% for phenanthrene), indicating that lipids compete for or block sorption sites on the organic matter. Sorption experiments on one pair of HF-treated soils indicated that the blocking effects of minerals and lipids are independent, since lipid extraction and HF-treatment combined increased K(OC) by more than either treatment alone. Lipids extracted from whole and HF-treated soils were very similar in composition, consisting predominantly of long-chain polymethylene structures. K(OC) of the lipid itself was lower than for any of the whole soils and soil fractions (lipid extracted and HF-treated) for diuron, but higher for phenanthrene. Solid-state (13)C NMR spectra of the HF-treated soils before and after lipid extraction indicated that 15-20% of alkyl C was removed by ASE and that no other structures were affected.

Even though it is well established that soil C content is the primary determinant of the sorption affinity of soils for non-ionic compounds, it is also clear that organic carbon-normalized sorption coefficients (K(OC)) vary considerably between soils. Two factors that may contribute to K(OC) variability are variations in organic matter chemistry between soils and interactions between organic matter and soil minerals. Here, we quantify these effects for two non-ionic sorbates-diuron and phenanthrene. The effect of organic matter-mineral interactions were evaluated by comparing K(OC) for demineralized (HF-treated) soils, with K(OC) for the corresponding whole soils. For diuron and phenanthrene, average ratios of K(OC) of the HF-treated soils to K(OC) of the whole soils were 2.5 and 2.3, respectively, indicating a substantial depression of K(OC) due to the presence of minerals in the whole soils. The effect of organic matter chemistry was determined by correlating K(OC) against distributions of C types determined using solid-state (13)C NMR spectroscopy. For diuron, K(OC) was positively correlated with aryl C and negatively correlated with O-alkyl C, for both whole and HF-treated soils, whereas for phenanthrene, these correlations were only present for the HF-treated soils. We suggest that the lack of a clear effect of organic matter chemistry on whole soil K(OC) for phenanthrene is due to an over-riding influence of organic matter-mineral interactions in this case. This hypothesis is supported by a correlation between the increase in K(OC) on HF-treatment and the soil clay content for phenanthrene, but not for diuron.

The potential of mid-infrared (MIR) spectroscopy in combination with partial least-squares (PLS) regression was investigated to predict the soil sorption (distribution) coefficient (K(d)) of a nonionic pesticide (diuron). A calibration set of 101 surface soils collected from South Australia was utilized for reference sorption data and MIR spectra. Principal component analysis (PCA) was performed on the spectra to detect spectral outliers. The MIR-PLS model was developed and validated by dividing the initial data set into four validation sets. The model resulted in a coefficient of determination (R2) of 0.69, a standard error (SE) of 5.57, and a residual predictive deviation (RPD) of 1.63. The normalized sorption coefficient for the organic compound (K(oc)) approach, on the other hand, resulted in R2, SE, and RPD values of 0.42, 7.26, and 1.25, respectively. However, the significant statistical difference between the two models was mainly due to two outliers detected via PCA. Apart from spectral outliers, the performance of the two models was essentially similar for the rest of the calibration set. Outlier detection by the MIR-PLS model may gainfully be employed as a tool for improving prediction of K(d). The MIR-based model can provide a direct estimation of K(d) values based on the integrated properties of organic and mineral matter reflected in the infrared spectra.

Organic matter has long been recognized as the main sorbent phase in soils for hydrophobic organic compounds (HOCs). In recent times, there has been an increasing realization that not only the amount, but also the chemical composition, of organic matter can influence the sorption properties of a soil. Here, we show that the organic carbon-normalized sorption coefficient (K(OC)) for diuron is 27-81% higher in 10 A11 horizons than in 10 matching A12 horizons for soils collected from a small (2ha) field. K(OC) was generally greater for the deeper (B) horizons, although these values may be inflated by sorption of diuron to clays. Organic matter chemistry of the A11 and A12 horizons was determined using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. K(OC) was positively correlated with aryl C (r2=0.59, significance level 0.001) and negatively correlated with O-alkyl C (r2=0.84, significance level <0.001). This is only the second report of correlations between whole soil K(OC) and NMR-derived measures of organic matter chemistry. We suggest that this success may be a consequence of limiting this study to a very small area (a single field). There is growing evidence that interactions between organic matter and clay minerals strongly affect K(OC). However, because the soil mineralogy varies little across the field, the influence of these interactions is greatly diminished, allowing the effect of organic matter chemistry on K(OC) to be seen clearly. This study in some way reconciles studies that show strong correlations between K(OC) and the chemistry of purified organic materials and the general lack of such correlations for whole soils.

Charcoal derived from the partial combustion of vegetation is ubiquitous in soils and sediments and can potentially sequester organic contaminants. To examine the role of charcoal in the sorption and desorption behaviors of diuron pesticide in soil, synthetic charcoals were produced through carbonization of red gum (Eucalyptus spp.) wood chips at 450 and 850 degrees C (referred to as charcoals BC450 and BC850, respectively, in this paper). Pore size distribution analyses revealed that BC850 contained mainly micropores (pores approximately 0.49 nm mean width), whereas BC450 was essentially not a microporous material. Short-term equilibration (< 24 h) tests were conducted to measure sorption and desorption of diuron in a soil amended with various amounts of charcoals of both types. The sorption coefficients, isotherm nonlinearity, and apparent sorption-desorption hysteresis markedly increased with increasing content of charcoal in the soil, more prominently in the case of BC850, presumably due to the presence of micropores and its relatively higher specific surface area. The degree of apparent sorption-desorption hystersis (hysteresis index) showed a good correlation with the micropore volume of the charcoal-amended soils. This study indicates that the presence of small amounts of charcoal produced at high temperatures (e.g., interior of wood logs during a fire) in soil can have a marked effect on the release behavior of organic compounds. Mechanisms of this apparent hysteretic behavior need to be further investigated.

To better understand the environmental fate of pesticides in Sri Lankan soils, we studied the sorption behavior of two commonly used pesticides (carbofuran and diuron) in 43 surface soils representing a range of soil physicochemical properties from dry and wet zones of Sri Lanka. For carbofuran, the K(d) (L/kg) values varied from 0.11 to 4.1 (mean, 0.83; median, 0.62) and K(oc) ranged from 7.3 to 120.6 (mean, 41.65; median, 36.1), whereas for diuron K(d) values varied from 0.5 to 75 (mean, 9.6; median, 5.15) and K(oc) ranged from 55.3 to 962 (mean, 407; median, 328). A comparison of sorption data on these tropical soils with published studies (mostly European and north American soils) showed that the ranges of sorption coefficients from Sri Lankan soils were within the wide range of K(oc) values reported in the literature. However, these values for both pesticides in soils from dry zones of Sri Lanka were consistently higher (up to two times) than those from the wet zone. The wide range of K(oc) values in Sri Lankan soils may be due to the possible difference in the nature of soil organic carbon, which needs to be further investigated.

Abstract: 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. [Copyright &y& Elsevier]