Polycyclic aromatic hydrocarbons (PAHs), abundant in mixed contaminant sites, often coexist with heavy metals. The fate and remediation of PAHs depend heavily on the sorption and desorption behavior of these contaminants. The sorption behavior can in turn be highly affected by certain soil components and properties, such as soil organic matter (SOM) and the presence of heavy metals. Through review of the literature focused on research from 2006 to 2018, this paper discusses interactions, challenges, influencing factors and potential synergies in sorption/desorption of mixed PAHs and heavy metal contamination of soil. The presence of either natural organic matter or heavy metals can enhance the sorption capability of fine soil, retarding the PAHs in the solid matrix. The co-existence of SOM and heavy metals has been reported to have synergistic effect on PAHs sorption. Enhanced and surfactant desorption of PAHs are also affected by the presence of both SOM and metals. Remediation techniques for PAHs removal from soil, such as soil washing, soil flushing and electrokinetics, can be affected by the presence of SOM and heavy metals. More detailed studies on the simultaneous effects of soil components and properties on the sorption/desorption of PAHs are needed to enhance the effectiveness of PAHs remediation technologies.

Corresponding author. fax: +49 381 498 2159. E-mail address: [email protected] (B. Lennartz). | International audience | This work was initiated to study the effects of climate induced soil water status variations which can reach extreme values under natural conditions on the sorption process of hydrophobic organic compounds. Based on the classical slurry batch methodology an approach is developed that allows the fast and careful complete drying of soil suspensions (microwave technique). Classical adsorption experiments were followed by three desorption steps with and without drying cycles. Drying and re-wetting enhanced the sorption-desorption hysteresis and Freundlich adsorption coefficients increased from 5.9 to 16 and 5.2 to 21 over three drying cycles for diuron and terbuthylazine respectively. Assuming the validity of a dual stage adsorption process, model evaluation suggests that drying is as a shrinking-like process leading to conformational changes of the dominant sorbent (soil organic matter) which restrict the intra-micro-particle diffusion. Rewetting only leads to a partial recovery of the diffusional pore space.

Corresponding author. fax: +49 381 498 2159. E-mail address: [email protected] (B. Lennartz). | International audience | This work was initiated to study the effects of climate induced soil water status variations which can reach extreme values under natural conditions on the sorption process of hydrophobic organic compounds. Based on the classical slurry batch methodology an approach is developed that allows the fast and careful complete drying of soil suspensions (microwave technique). Classical adsorption experiments were followed by three desorption steps with and without drying cycles. Drying and re-wetting enhanced the sorption-desorption hysteresis and Freundlich adsorption coefficients increased from 5.9 to 16 and 5.2 to 21 over three drying cycles for diuron and terbuthylazine respectively. Assuming the validity of a dual stage adsorption process, model evaluation suggests that drying is as a shrinking-like process leading to conformational changes of the dominant sorbent (soil organic matter) which restrict the intra-micro-particle diffusion. Rewetting only leads to a partial recovery of the diffusional pore space.

The contamination of paddy soils is of great concern since it links to human health via food supply. Limited knowledge is available on PCB residue characteristics and the associated health risks in paddy soils under various environmental conditions. In this study, a soil sampling campaign was conducted in three typical paddy fields, i.e., Sanjiang Plain (SP), Taihu Plain (TP) and Hani Terrace (HT), crossing a transect of 4000 km in China. The concentrations of 29 quantified PCBs varied from 58.6 to 1930 pg/g in paddy soils, with samples at TP showing the highest burden. Tri-CBs were the major homologue group at SP and HT, whereas hexa-CBs at TP. Altitude, temperature, soil organic matter content and soil conductivity well explained the variations in PCB concentrations among sites. The homologue profiles of soil PCBs followed the fractionation theory. In addition, soil conductivity was found to be negatively correlated to low-chlorinated PCBs and positively to high-chlorinated congeners. Furthermore, the toxicities of soil PCBs and the exposure risks through rice intake were estimated. Higher toxicity equivalent quantities and hazard indexes were found at SP than TP and HT, with over one third of the samples displaying health risks. The results of this work highlight the necessity to better understand the occurrence characteristics and the associated health risks of PCBs in soils of rice-growing regions.

The Yellow River is the second largest river in China. Carbon transport by the Yellow River has significant influence on riverine carbon cycles in Asia. During the wet season, the riverine carbon was mainly found in dissolved form, i.e., dissolved organic carbon (DOC), along the entire course of the river. The distinct spatial variations of DOC concentration were observed at different reaches of the mainstream (p < 0.01), while the highest mean DOC concentration was generally observed at midstream (4.13 ± 0.91 mg/L). Carbon stable isotope analysis δ¹³C and C: N ratio of DOC, evidenced the sources of DOC in headwater and upstream were primarily the terrestrial plants (94% and 61%), but it was changed to soil organic matter (SOM) in mid- and downstream (36% and 37%), and the contribution of sewage to DOC were also increased to 17% and 18%. In the whole mainstream of the Yellow River, water temperature (WT) had a significant impact on DOC concentration, and it could explain 67% of the DOC variance. However, in a large catchment, the driving mechanisms on the DOC variations in headwaters will not necessarily be those controlling DOC trends in downstream. The study firstly quantified, in headwater and upstream, the natural factors explained as much as 65% and 73% of the DOC variations, respectively. In mid- and downstream areas, DOC was significantly influenced by the amount of wastewater discharged by the industry and the use of chemical fertilizers (p < 0.05). These findings may facilitate a better assessment of global riverine carbon cycling and may help to reveal the importance of the balance between development and environmental sustainability with the changing DOC transport features in the Yellow River due to human disturbances.

Nitrogen (N) addition and mowing can significantly influence micronutrient cycling in grassland ecosystems. It remains largely unknown about how different forms of added N affect micronutrient status in plant-soil systems. We examined the effects of different N compounds of (NH₄)₂SO₄, NH₄NO₃, and urea with and without mowing on micronutrient Fe, Mn, Cu, and Zn in soil-plant systems in a meadow steppe. The results showed that (NH₄)₂SO₄ addition had a stronger negative effect on soil pH compared with NH₄NO₃ and urea, resulting in higher increases in soil available Fe and Mn herein. Nitrogen addition decreased plant community-level biomass weighted (hereafter referred to as community-level) Fe concentration but increased Mn concentration, with a greater effect under (NH₄)₂SO₄ addition. Community-level Cu concentration increased with (NH₄)₂SO₄ and NH₄NO₃ addition only under mowing treatment. Mowing synergistically interacted with urea addition to increase community-level Mn and Zn concentrations even with decreased soil organic matter, possibly because of compensatory plant growth and thus higher plant nutrient uptake intensity under mowing treatment. Overall, responses of plant-soil micronutrients to N addition varied with mowing and different N compounds, which were mainly regulated by soil physicochemical properties and plant growth. Different magnitude of micronutrient responses in plants and soils shed light on the necessity to consider the role of various N compounds in biogeochemical models when projecting the effects of N enrichment on grassland ecosystems.

Agricultural products from seleniferous areas commonly face problems associated with substantial variation in selenium (Se) concentration, which is mainly caused by the heterogeneity of Se bioavailability in soil. Many studies have assessed the bioavailability of Se and its influencing factors using soil samples treated with exogenous Se. Given the distinctly different characteristics of Se-spiked soils and naturally seleniferous soils, exploring Se bioavailability in naturally seleniferous soils is crucial to the stable production of Se-enriched agricultural products. In this study, we used the classical sequential extraction method to determine the Se fractionation and then applied the diffusive gradients in thin-films (DGT) technique to assess the Se bioavailability in naturally seleniferous soils. The results indicated that soluble and exchangeable Se fractions with high bioavailability accounted for only 0.7% and 5.1% of total Se, respectively. Both soluble and exchangeable Se concentrations were significantly positively correlated with soil pH (r = 0.329 and 0.262, respectively; P < 0.01). Se mainly exists in Fe–Mn oxide-bound, organic matter-bound, and residual Se fractions with low mobility (94.2% of total Se), among which organic matter-bound Se was the predominant fraction (49.5% of total Se). A significant positive correlation was found between total Se and soil organic matter (r = 0.539; P < 0.01). Multiple regression analysis revealed that the DGT-determined Se was mostly derived from soluble and exchangeable Se. The high correlation between the DGT-determined Se fraction and Se uptake by rice (r = 0.91; P < 0.01) confirmed that DGT can accurately assess Se bioavailability in naturally seleniferous soils in Enshi and other similar environmental settings.

The on-going and extensive use of neonicotinoids occur in orchards. However, it is still unknown whether and how orchard management affects soil properties, especially the contents and structure of soil organic matter during orchard development, and their further influences on neonicotinoid persistence. Here, surface soil samples were collected from the citrus orchards with different cultivation ages (1, 10, 14, and 20 years), and their physicochemical properties were determined. Changes in the chemical structure of soil organic matter (SOM) were furtherly examined using solid-state CP/TOSS ¹³C NMR. Then, the sorption isotherms of imidacloprid in these soils were investigated. The sorption coefficient (Kd) of imidacloprid at Cₑ of 0.05 mg/L in the orchard soils increased by 19.4–23.3%, along a 20-year chronosequence of cultivation, which should be mainly ascribed to the increase of SOM. However, the organic carbon-normalized sorption coefficient (Kₒc, sorption per unit mass of OM) of imidacloprid declined with increasing cultivation ages. Moreover, the polar and aliphatic domains of SOM had a significantly positive relation to the Kₒc of imidacloprid, suggesting its key role in governing imidacloprid sorption. The results highlighted that reasonable management measures could be adopted to control the occurrence and fate of neonicotinoids in soils, mainly by affecting the content and quality of SOM.

High-density samples are usually a prerequisite for obtaining high-precision source apportionment results in large-scale areas. In-situ field portable X-ray fluorescence spectrometry (FPXRF) is a fast and cheap way to increase the sample size of soil heavy metals (HMs). Moreover, categorical land-use types may be closely associated with source contributions. However, the above information has rarely been incorporated into the source apportionment. In this study, robust geographically weighted regression (RGWR) was first used to correct the spatially varying effect of the related soil factors (e.g., soil water and soil organic matter) on in-situ FPXRF in an urban-rural fringe of Wuhan City, China, and the correction accuracy of RGWR was compared with those of the traditionally non-spatial multiple linear regression (MLR) and basic GWR. Then, the effect of land-use types on HM concentrations was partitioned using analysis of variance (ANOVA). Last, based on the robust spatial receptor model (i.e., robust absolute principal component scores/RGWR [RAPCS/RGWR]), this study proposed RAPCS/RGWR with categorical land-use types and RGWR-corrected in-situ FPXRF data (RAPCS/RGWR_LU&FPXRF), and its performance was compared with those of RAPCS/RGWR with none or one kind of auxiliary data. Results showed that (i) the performances of the correction models for in-situ FPXRF data were in the order of RGWR > GWR > MLR, and the relative improvement of RGWR over MLR ranged from 52.6% to 70.71% for each HM; (ii) categorical land-use types significantly affected the concentrations of soil Zn, Cu, As, and Pb; (iii) the highest estimation accuracy for source contributions was obtained by RAPCS/RGWR_LU&FPXRF, and the lowest estimation accuracy was obtained by basic RAPCS/RGWR. It is concluded that land-use types and RGWR-corrected in-situ FPXRF data are closely associated with the source contribution, and RAPCS/RGWR_LU&FPXRF is a cost-effective source apportionment method for soil HMs in large-scale areas.