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Researchers measured the soil organic matter (SOM) structural composition of 27 diverse soils in Pakistan and Australia. Researchers believe that the aromatic quality of the soil organic matter will tell whether or not the soil can bind to nonionic pesticides. Tables illustrate soil quality and research findings.

The potential of mid-infrared (MIR) spectroscopy in combination with partial least-squares (PLS) regression was investigated to predict the soil sorption (distribution) coefficient (Kd) 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 (Koc) 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 Kd. The MIR-based model can provide a direct estimation of Kd values based on the integrated properties of organic and mineral matter reflected in the infrared spectra. [ABSTRACT FROM AUTHOR]

We investigated how the NMR properties of uniformly 13C-labeled benzene molecules are influenced by sorption to charcoals produced in the laboratory and collected from the field following wildfires. Uniformly 13C-labeled benzene was sorbed to two charcoals produced in the laboratory at 450 and 850 °C. The chemical shift of benzene sorbed to the higher-temperature charcoal was 5–6 ppm lower than that of benzene sorbed to the lower-temperature charcoal. This difference was attributed to stronger diamagnetic ring currents (which cause a shift to lower ppm values) in the more condensed or ‘graphitic’ high-temperature charcoal. The chemical shift of benzene sorbed to two charcoals collected from the field following wildfires indicated a degree of charcoal graphitization intermediate between that of the two laboratory-prepared charcoals. Variable contact time and dipolar dephasing experiments showed that the molecular mobility of sorbed benzene molecules increased with increasing charcoal graphitization, and also increased with increasing benzene concentration. We propose that the chemical shift displacement of molecules sorbed to charcoal could be used to identify molecules sorbed to black carbon in heterogeneous matrixes such as soils and sediments, and to establish how condensed or ‘graphitic’ the black carbon is. [ABSTRACT FROM AUTHOR]

Microbial reduction of Fe(lll) in illite was studied to evaluate the possibility of microbial utilization of Fe(lll) in sedimentary clays and to determine the effects of bioreduction on clay composition and structure. A subsurface bacterium (Shewanella putrefaciens CN32) and illite separates (<0.2 µm) from St. Peter Formation sandstone in 0gle County, IL, were used in laboratory experiments. Illite suspensions buffered at pH 7 with bicarbonate were inoculated with CN32 and provided with H[sub 2] as an electron donor. In selected treatments, anthraquinone-2,6-disulfonate (AQDS), was included as an electron shuttle to facilitate the bioreduction. Fe(ll) production in inoculated treatments was determined by extraction with 0.5 N HCl and compared to uninoculated controls to establish the extent of biological reduction. The resulting solids were characterized by Mössbauer spectroscopy and scanning and transmission electron microscopy (SEM and TEM). The characterization of the starting illite material revealed that it contained a minor component of goethite (α-Fe00H) in addition to fibrous illite. The starting material (both goethite and illite) contained 6% (w/ w) total Fe, and 82% of the total Fe was Fe(lll). Approximately 30% of total Fe was associated with goethite. At the end of a 30-day incubation, residual goethite and illite remained. The extent of reduction was much greater in the presence of AQDS (25%) than in its absence (0%). Modeling of Mössbauer spectra of the bioreduced material indicated that both goethite and illite were reduced but to a different extent. Additionally, TEM evidence suggested that there was a dramatic change in illite morphology upon bioreduction from fibrous needles to plates. The ability of bacteria to utilize Fe(lll) in illite has important implications for microbial functions and survival mechanisms, as well as many geological processes, in the subsurface. [ABSTRACT FROM AUTHOR]

This study investigated the mobilization of a wide range of per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foams (AFFFs) in water-saturated soils through one-dimensional (1-D) column experiments with a view to assessing the feasibility of their remediation by soil desorption and washing. Results indicated that sorption/desorption of most of the shorter-carbon-chain PFASs ( C ≤ 6) in soil reached greater than 99% rapidly─after approximately two pore volumes (PVs) and were well predicted by an equilibrium transport model, indicating that they will be readily removed by soil washing technologies. In contrast, the equilibrium model failed to predict the mobilization of longer-chain PFASs ( C ≥ 7), indicating the presence of nonequilibrium sorption/desorption (confirmed by a flow interruption experiment). The actual time taken to attain 99% sorption/desorption was up to 5 times longer than predicted by the equilibrium model (e.g., ∼62 PVs versus ∼12 PVs predicted for perfluorooctane sulfonate (PFOS) in loamy sand). The increasing contribution of hydrophobic interactions over the electrostatic interactions is suggested as the main driving factor of the nonequilibrium processes. The inverse linear relationship ( R 2 = 0.6, p < 0.0001) between the nonequilibrium mass transfer rate coefficient and the Freundlich sorption coefficient could potentially be a useful means for preliminary evaluation of potential nonequilibrium sorption/desorption of PFASs in soils.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil-water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF 2 ≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

Plant protection products containing nanomaterials that alter the functionality or risk profile of active ingredients (nano-enabled pesticides) promise many benefits over conventional pesticide products. These benefits may include improved formulation characteristics, easier application, better targeting of pest species, increased efficacy, lower application rates, and enhanced environmental safety. After many years of research and development, nano-enabled pesticides are starting to make their way into the market. The introduction of this technology raises a number of issues for regulators, including how does the ecological risk assessment of nano-enabled pesticide products differ from that of conventional plant protection products? In this paper, a group drawn from regulatory agencies, academia, research, and the agrochemicals industry offers a perspective on relevant considerations pertaining to the problem formulation phase of the ecological risk assessment of nano-enabled pesticides.

Nanopesticides or nano plant protection products represent an emerging technological development that, in relation to pesticide use, could offer a range of benefits including increased efficacy, durability, and a reduction in the amounts of active ingredients that need to be used. A number of formulation types have been suggested including emulsions (e.g., nanoemulsions), nanocapsules (e.g., with polymers), and products containing pristine engineered nanoparticles, such as metals, metal oxides, and nanoclays. The increasing interest in the use of nanopesticides raises questions as to how to assess the environmental risk of these materials for regulatory purposes. Here, the current approaches for environmental risk assessment of pesticides are reviewed and the question of whether these approaches are fit for purpose for use on nanopesticides is addressed. Potential adaptations to existing environmental risk assessment tests and procedures for use with nanopesticides are discussed, addressing aspects such as analysis and characterization, environmental fate and exposure assessment, uptake by biota, ecotoxicity, and risk assessment of nanopesticides in aquatic and terrestrial ecosystems. Throughout, the main focus is on assessing whether the presence of the nanoformulation introduces potential differences relative to the conventional active ingredients. The proposed changes in the test methodology, research priorities, and recommendations would facilitate the development of regulatory approaches and a regulatory framework for nanopesticides.

This study explored the potential of mid-infrared spectroscopy (MIR) with partial least-squares (PLS) analysis to predict sorption coefficients (Kd) of pesticides in soil. The MIR technique has the advantage of being sensitive to both the content and the chemistry of soil organic matter and mineralogy, the important factors in the sorption of nonionic pesticides. MIR spectra and batch Kd values of atrazine were determined on a set of 31 soil samples as reference data for PLS calibration. The samples, with high variability in soil organic carbon content (SOC), were chosen from 10 southern Australian soil profiles (A1, A2, B, and C in one case). PLS calibrations, developed for the prediction of Kd from the MIR spectra and reference Kd data, were compared with predictions from Koc-based indirect estimation using SOC content. The reference Kd data for the 31 samples ranged from 0.31 to 5.48 L/kg, whereas Koc ranged from 30 to 680 L/kg. Both coefficients generally increased with total SOC content but showed a relatively poor coefficient of determination (R2 = 0.53; P > 0.0001) and a high standard error of prediction (SEP =1.22) for the prediction of Kd from Koc. This poor prediction suggested that total SOC content alone could explain only half of the variation in Kd. In contrast, the regression plot of PLS predicted versus measured Kd resulted in an improved correlation, with R2 = 0.72 ( P > 0.0001) and standard error of cross-validation (SECV) = 0.63 for three PLS factors. With the advantages of MIR-PLS in mind, (i) more accurate prediction of Kd, (ii) an ability to reflect the nature and content of SOC as well as mineralogy, and (iii) high repeatability and throughput, it is proposed that MIR-PLS has the potential for an improved and rapid assessment of pesticide sorption in 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.

The sorption behavior of diuron, imidacloprid, and thiacloprid was investigated using 22 soils collected in triplicate from temperate environments in Australia and tropical environments in Australia and the Philippines. Within the temperate environment in Australia, the soils were selected from a range of land uses. The average KOC values (L/kg) for imidacloprid were 326, 322, and 336; for thiacloprid, the values were 915, 743, and 842; and for diuron, the values were 579, 536, and 618 for the Ord (tropical), Mt. Lofty (temperate), and Philippines (tropical) soils, respectively. For all soils, the sorption coefficients decreased in the following order: thiacloprid > diuron > imidacloprid. There were no significant differences in sorption behavior between the tropical soils from the Philippines and the temperate soils from Australia. Sorption was also not significantly related with soil characteristics, namely, organic carbon (OC) content, clay content, and pH, for any of the three chemicals studied. When the data were sorted into separate land uses, the sorption of all three chemicals was highly correlated (P < 0.001) with OC for the rice soils from the Philippines. Sorption coefficients for all three chemicals were highly correlated with OC in temperate, native soils only when one extreme value was removed. The relationships between sorption of all three chemicals and OC in temperate, pasture soils were best described by a polynomial. Sorption coefficients for imidacloprid and thiacloprid determined in the temperate pasture soils remained fairly consistent as the OC content increased from 3.3 to 5.3%, indicating that, although the total OC in the pasture soils was increasing, the component of OC involved with sorption of these two compounds may have been remaining constant. This study demonstrated that the origin of the soils (i.e., temperate vs tropical) had no significant effect on the sorption behavior, but in some cases, land use significantly affected the sorption behavior of the three pesticides studied. The impact of land use on the nature of soil OC will be further investigated by NMR analysis.