Modeling of Cs migration in soils using an 80-year soil archive: role of fertilizers and agricultural amendments

An 80-year soil archive, the 42-plot experimental design at the INRA in Versailles (France), is used here to study long-term contamination by ¹³⁷Cs atmospheric deposition and the fate of this radioisotope when associated with various agricultural practices: fallow land, KCl, NH₄(NO₃), superphosphate fertilizers, horse manure and lime amendments. The pertinence of a simple box model, where radiocaesium is supposed to move downward by convectional mechanisms, is checked using samples from control plots which had been neither amended, nor cultivated since 1928. This simple model presents the advantage of depending on only two parameters: α, a proportional factor allowing the historical atmospheric ¹³⁷Cs fluxes to be reconstructed locally, and k, an annual loss coefficient from the plow horizon. Another pseudo-unknown is however necessary to run the model: the shape of historical ¹³⁷Cs deposition, but this function can be easily computed by merging several curves previously established by other surveys. A loss of ∼1.5% per year from the plow horizon, combined with appropriate fluxes, provides good concordance between simulated and measured values. In the 0–25 cm horizon, the residence half time is found to be ∼18 yr (including both migration and radioactive decay). Migration rate constants are also calculated for some plots receiving continuous long-term agricultural treatments. Comparison with the control plots reveals significant influence of amendments on ¹³⁷Cs mobility in these soils developed from a unique genoform.     

“Modern agriculture” transfers many pesticides to watercourses: a case study of a representative rural catchment of southern Brazil

Environmental Science and Pollution Research - The total cultivated area in Brazil reached to 62 million ha in 2018, with the predominance of genetically modified soybean and corn (36 and 17...     

Anthropogenic lead distribution in soils under arable land and permanent grassland estimated by Pb isotopic compositions

The role of land use on fate of metals in soils is poorly understood. In this work, we studied the incorporation of lead in two neighboring soils with comparable pedogenesis but under long-term different agricultural management. Distributions of anthropogenic Pb were assessed from concentrations and isotopic compositions determined on bulk horizon samples, systematical 5-10 cm increment samples, and on 24-h EDTA extracts. Minor amounts of anthropogenic lead were detected until 1-m depth under permanent grassland, linked to high earthworm activity. In arable land, exogenous Pb predominantly accumulated at depths <60 cm. Although the proximity between the two sites ensured comparable exposition regarding atmospheric Pb deposition, the isotopic compositions clearly showed the influence of an unidentified component for the cultivated soil. This work highlights the need for exhaustive information on historical human activities in such anthropized agrosystems when fate of metal pollution is considered.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Interaction of erythromycin ethylsuccinate and acetaminophen with protein fraction of extracellular polymeric substances (EPS) from various bacterial aggregates

Extracellular polymeric substances (EPS) are, along with microbial cells, the main components of the biological sludges used in wastewater treatment and natural biofilms. EPS play a major role in removing pollutants from water by means of sorption. The ability of soluble EPS (S-EPS) and bound EPS (B-EPS) derived from various bacterial aggregates (flocs, granules, biofilms) to bind at pH 7.0?±?0.1 to two pharmaceutical substances, acetaminophen (ACE) and erythromycin ethylsuccinate (ERY), has been investigated using the fluorescence quenching method. Two intense fluorescence peaks, A (Ex/Em range, 200–250/275–380 nm) and B (Ex/Em range, 260–320/275–360 nm), corresponding respectively to the aromatic protein region and soluble microbial by-product-like region, were identified in a three-dimensional excitation-emission matrix of EPS samples. The fluorescence peak, which corresponds to humic-like substances, was also identified though at low intensity. The ability of EPS to bind ACE was found to exceed that for ERY. The aromatic protein fraction of EPS displays a slightly higher affinity for drugs than that shown by the soluble microbial by-product-like fraction. The S-EPS and B-EPS present the same affinity for ACE and ERY. The effective quenching constants (log K) derived from the Stern–Volmer Equation equaled at peak A (with S-EPS): 3.7?±?0.2 to 4.0?±?0.1 for ACE and 2.1?±?0.3 to 2.7?±?0.1 for ERY. With B-EPS, these values were 3.9?±?0.1 to 4.0?±?0.1 for ACE and 2.0?±?0.2 to 2.6?±?0.1 for ERY. Our results suggest that the weaker EPS affinity for ERY than for ACE serves to partially explain why only about 50–80 % of ERY is removed from wastewater at the treatment plant. Moreover, this work demonstrates that EPS from natural river biofilms are able to bind drugs, which in turn may limit the mobility of drugs in natural waters.     

Pharmaceutical compound removal efficiency by a small constructed wetland located in south Brazil

Environmental Science and Pollution Research - The fate of pharmaceuticals during the treatment of effluents is of major concern since they are not completely degraded and because of their...     

Sorption of selected pharmaceuticals by a river sediment: role and mechanisms of sediment or Aldrich humic substances

Environmental Science and Pollution Research - Sorption of pharmaceuticals onto sediments is frequently related to organic matter content. Thus, the present work aimed to compare the effect of...     

Fate of metal-associated POM in a soil under arable land use contaminated by metallurgical fallout in northern France

Organic matter is a major metal-retaining constituent in soils. Among the diversity of organic components in soils, particulate organic matter (POM) accumulates large amounts of metals, but the fate of such metal-associated POM is unknown. We studied different POM size fractions and their corresponding mineral size-fractions isolated from the surface horizon of a soil affected by metallurgical fallout. Analyses of total and EDTA extractible metal contents performed on all size fractions demonstrated that with decreasing POM size, larger metal concentrations were observed but they were less extractable. Micromorphological study revealed the occurrence of opaque parts in decaying POM fragments and their individualization as fine, irregularly shaped opaque fragments in the soil matrix. This work suggested a mutual sequestration of metal pollutants and organic carbon as micro-meter sized, metal-enriched organic particles derived from POM, representing an original pathway for natural attenuation of risk related to metal contaminated soils.     

Changes in soil organic matter chemical properties after organic amendments

Organic inputs are used to improve soil physical and chemical properties, but the corresponding changes in soil organic matter (SOM) chemical properties are not well known. In this study, we compared some characteristics of the SOM of a soil receiving either no organic inputs, or two different amendments during 15 years (straw or conifer compost). Quantities of organic carbon and C/N values were determined on particle size fractions after physical soil fractionation to localize changes due to amendments. Contents in reactive functional groups, acid-base properties and copper binding affinities were determined by titration experiments for the soluble fraction of SOM: the fulvic acid fraction (FA). Data of FA extracted from the bulk soil were compared to data of FA extracted from the <20 microm size fraction with the help of either a discrete or a continuous model (fit of data with FITEQL or NICA, respectively). Copper binding characteristics of FA extracted from the <20 microm size fraction did not change significantly after organic inputs, while those of FA extracted from the bulk organic-amended soils were found different from the ones with no amendment. Minor effects observed in the finer soil fractions were ascribed to their low turn-over of organic carbon and/or to a greater homogeneity in the nature of the organic carbon entering these fractions. Our results show major chemical changes in coarser soil organic fractions after organic amendments.     

Combination of biodegradable organic matter quantification and XAD-fractionation as effective working parameter for the study of biodegradability in environmental and anthropic samples

The present work proposes to couple quantification of biodegradable organic matter (BOM) with XAD-fractionation. Biodegradable dissolved organic carbon (BDOC) and assimilable organic carbon (AOC) analysis were applied to fractions extracted by XAD resin. An examination of mechanisms during consumption of BOM has been carried out, using comparison of biodegradability between the bulk BOM of samples (landfill leachate and surface water) and the sum of BOM contents obtained for the extracted fractions. Results point out that a cometabolism mechanism seems to be involved during the degradation of the surface water fractions. On the other hand, fractions extracted from the leachate seem to be degraded as primary substratum. The more reactive fractions of the leachate (HPO*) and the water (HPI) have been identified as well the less reactive (HPI* and HPO, respectively). The BDOC contents determined for the bulk leachate and surface water are 10+/-2% and 28+/-2%, respectively. The values of AOC are 107+/-18 microg C acetate L(-1) and 163+/-21 microg C acetate L(-1), respectively.