Finding an environment-friendly and affordable method to remove contaminated soils from Polycyclic Aromatic Hydrocarbons (PAHs) has now become an attractive field for researchers, with super-critical fluid extraction being an innovative process in the field of contaminated soil treatment. Extraction with super-critical fluid is a simple and rapid extraction process that uses super-critical fluids as solvents. The present study has investigated the extraction of contaminated soil with Polycyclic Aromatic Hydrocarbons (PAHs) by means of batch supercritical water reactor, employing variables like pressure (100–300 bar), temperature (60–140 ◦C), residence time (0.5–3 hours), and base, acidic, and neutral pH values. In order optimize the process parameters, Response Surface Methodology (RSM) has been used. Results show that removal efficiency of PAHs is between 82%-100%, where the highest PAHs removal efficiency (100%) has been observed in Test No. 22, with a pressure of 300 bars, temperature of 500°C, acidic pH equal to 5, and duration of 3 hours. In addition, the lowest removal efficiency of these compounds (82%) has been obtained in Test No. 26, with a pressure of 300 bars, temperature of 350°C, base pH of 9, and duration of half an hour. According to the results from this study, it has become clear that residence time is the most important and most effective parameter for removing PAHs from contaminated soil. Afterwards, temperature and pH are most influential with pressure showing the least effect. Using supercritical water method in appropriate conditions can eliminate more than 99% of aromatic contamination.

Diethyl phthalate (DEP), as a kind of universally used plasticizer, has aroused considerable public concern owing to its wide detection, environmental stability, and potential health risks. In this work, the highly efficient removal of DEP by ferrate (VI) (Fe(VI)) was systematically explored in soil environment. The effects of the oxidant dosages, soil types, as well as the presence of coexisting cations and anions in tested soil on DEP removal were evaluated. When the dosage of Fe(VI) was 20 mM, complete removal of DEP (50 μg/g) was achieved in the tested soil after 2 min of reaction. Furthermore, the removal rate of DEP was closely related to the soil types, and the degradation rates were decreased obviously in red soil (RS), black soil (BS) and paddy soil (PS), probably due to the acidic condition and high content of organic matters. Moreover, the presence of Ca²⁺, Mg²⁺ and Al³⁺ in soil can inhibit the removal of DEP by Fe(VI), while SO₄²⁻ has an slightly promotion effect. Six oxidation intermediates were detected in the reaction process of DEP, product analysis revealed that the transformation of DEP was mainly through two pathways, including hydrolysis and hydroxylation reactions, which were probably mediated by oxygen atom transfer process of Fe(VI). Based on the frontier electron density theory calculation, two ester groups of DEP were prone to be attacked by Fe(VI), and the hydroxyl addition tended to occur at the para-position of one of the ester groups on the benzene ring. This study provides a novel approach for phthalate esters removal from soil using Fe(VI) oxidation and shows new insights into the oxidation mechanisms.

Iron nanoparticles (Fe NPs) have often been used for in situ remediation of both groundwater and soil. However, the impact of Fe NPs on the distribution and transformation of As species in contaminated soil is still largely unknown. In this study, green iron oxide nanoparticles synthesized using a euphorbia cochinchinensis leaf extract (GION) were used to stabilize As in a contaminated soil. GION exhibited excellent As stabilization effects, where As in non-specifically-bound and specifically-bound fractions decreased by 27.1% and 67.3% after 120 days incubation. While both arsenate (As (V)) and arsenite (As (III)) decreased after GION application, As (V) remained the dominant species in soil. X-ray photoelectron spectroscopy (XPS) confirmed that As (V) was the dominant species in specifically-bound fractions, while As (III) was the dominant species in amorphous and poorly-crystalline hydrous oxides of Fe and Al. Correlation analysis showed that while highly available As fractions were negatively correlated to oxalate and DCB extractable Fe, they were positively correlated to Fe²⁺ content, which indicated that Fe cycling was the main process influencing changes in As availability. X-ray fluorescence (XRF) spectroscopy also showed that the Fe₂O₃ content increased by 47.9% following GION soil treatments. Overall, this work indicated that As would be transformed to more stable fractions during the cycling of Fe following GION application and that the application of GION, even in small doses, provides a low-cost and ecofriendly method for the stabilization of As in soil.

Biofumigation is an effective, non-chemical method to control soil-borne pests and diseases and to maximize crop yield. We studied the responses of soil bacterial and fungal communities, the soil’s nutritional state and strawberry yield, when the soil was biofumigated each year for five consecutive years using fresh chicken manure (BioFum). BioFum significantly increased the soil’s NH4+-N, NO3−-N, available P and K and organic matter. Fusarium spp. and Phytophthora spp. which are known to cause plant disease, were significantly decreased after BioFum. In addition, Biofum increased the soil’s temperature, enhanced chlorophyll levels in the leaves of strawberry plants, and the soluble sugar and ascorbic acid content in strawberry fruit. We used high-throughput gene sequencing to monitor changes in the soil’s bacterial and fungal communities. Although BioFum significantly decreased the diversity of these communities, it increased the relative abundance of some biological control agents in the phylum Actinobacteria and the genera Pseudomonas, Bacillus and Chaetomium. An increase in these biological control agents would reduce the incidence of soil-borne pathogens and plant disease. Although strawberry marketable yield using BioFum was higher in the first three years, the decline in the final two years could be due to the accumulation of P and K which may have delayed flowering and fruiting. Methods to overcome yield losses using BioFum need to be developed in the future. Our research, however, showed that BioFum enhanced soil fertility, reduced the presence of soil pathogens, increased the relative abundance of beneficial bacteria and fungi and improved strawberry quality. Unlike chemical soil treatments that can cause pest and disease resistance when used continuously over many years, our multi-year research program on BioFum showed that this treatment provided significant benefits to the soil, plant and strawberry fruit.

Production of chrysanthemum (Dendranthema grandiflora) in greenhouses often requires intensive pesticide use, which raises serious concerns over food safety and human health. This study investigated uptake, translocation and residue dissipation of typical fungicides (metalaxyl-M and fludioxonil) and insecticides (cyantraniliprole and thiamethoxam) in greenhouse chrysanthemum when applied in soils. Chrysanthemum plants could absorb these pesticides from soils via roots to various degrees, and bioconcentration factors (BCFLS) were positively correlated with lipophilicity (log Kₒw) of pesticides. Highly lipophilic fludioxonil (log Kₒw = 4.12) had the greatest BCFLS (2.96 ± 0.41 g g⁻¹), whereas hydrophilic thiamethoxam (log Kₒw = −0.13) had the lowest (0.09 ± 0.03 g g⁻¹). Translocation factors (TF) from roots to shoots followed the order of TFₗₑₐf > TFₛₜₑₘ > TFfₗₒwₑᵣ. Metalaxyl-M and cyantraniliprole with medium lipophilicity (log Kₒw of 1.71 and 2.02, respectively) and hydrophilic thiamethoxam showed relatively strong translocation potentials with TF values in the range of 0.29–0.81, 0.36–2.74 and 0.30–1.03, respectively. Dissipation kinetics in chrysanthemum flowers followed the first-order with a half-life of 21.7, 5.5, 10.0 or 8.2 days for metalaxyl-M, fludioxonil, cyantraniliprole and thiamethoxam, respectively. Final residues of these four pesticides, including clothianidin (a primary toxic metabolite of thiamethoxam), in all chrysanthemum flower samples were below the maximum residue limit (MRL) values 21 days after two soil applications each at the recommended dose (i.e., 3.2, 2.1, 4.3 and 4.3 kg ha⁻¹, respectively). However, when doubling the recommended dose, the metabolite clothianidin remained at concentrations greater than the MRL, despite that thiamethoxam concentration was lower than the MRL value. This study provided valuable insights on the uptake and residues of metalaxyl-M, fludioxonil, cyantraniliprole and thiamethoxam (including its metabolite clothianidin) in greenhouse chrysanthemum production, and could help better assess food safety risks of chrysanthemum contamination by parent pesticides and their metabolites.

About 11% of the global anthropogenic greenhouse gases (GHGs) emissions result from agricultural practices. Dairy manure (DM) application to soil is regarded as a best management practice due to C sequestration and improvement of soil physiochemical properties. However, GHGs emissions from the soil following the DM application could offset its advantages. Biochar (BC) is known to affect N transformation and GHGs emissions from soil. There had been considerably less focus on the BC amendment and its effects on GHGs emissions following DM application under field conditions. The objectives of this study were; i) to determine the temporal patterns and cumulative GHGs fluxes following DM and inorganic nitrogen (IN) application and, ii) to investigate BC amendment impact on DMY, GWP, direct N₂O emission factor (EFd) and the response of CH₄ emissions (RC) in DM based silage corn. To achieve these objectives a two-year field experiment was conducted with these treatments: 1) DM with high N conc. (DM₁: 0.37% N); 2) DM with low N conc. (DM₂: 0.13% N); 3) IN; 4) DM₁+BC; 5) DM₂+BC; 6) IN + BC; and 7) Control (N₀); and were laid out in randomized complete block design with four replications. BC amendment to DM₁, DM₂ and IN significantly reduced cumulative CO₂ emission by 16, 25.5 and 26.5%, CH₄ emission by 184, 200 and 293% and N₂O emission by 95, 86 and 93% respectively. It also reduced area-scaled and yield-scaled GWP, EFd, RC and enhanced DMY. Thus, BC application showed great potential to offset the negative effects of DM application i.e GHGs emissions from the silage corn cropping system. Further research is needed to evaluate soil organic carbon and nitrogen dynamics (substrates for GHG emissions) after DM and BC application on various soil types and cropping systems under field conditions.

An experiment was performed to explore the interactive impacts of zinc oxide nanoparticles (ZnO NPs) and cadmium (Cd) on growth, yield, antioxidant enzymes, Cd and zinc (Zn) concentrations in wheat (Triticum aestivum). The ZnO NPs were applied both in Cd-contaminated soil and foliar spray (in separate studies) on wheat at different intervals and plants were harvested after physiological maturity. Results depicted that ZnO NPs enhanced the growth, photosynthesis, and grain yield, whereas Cd and Zn concentrations decreased and increased respectively in wheat shoots, roots and grains. The Cd concentrations in the grains were decreased by 30–77%, and 16–78% with foliar and soil application of NPs as compared to the control, respectively. The ZnO NPs reduced the electrolyte leakage while increased SOD and POD activities in leaves of wheat. It can be concluded that ZnO NPs (levels used in the study) could effectively reduce the toxicity and concentration of Cd in wheat whereas increase the Zn concentration in wheat. Thus, ZnO NPs might be helpful in decreasing Cd and increasing Zn biofortification in cereals which might be effective to reduce the hidden hunger in humans owing the deficiency of Zn in cereals.

The effects of wastewater irrigation and sewage sludge on the dissipation behavior of the fungicide benalaxyl and its primary metabolite benalaxyl acid in soil were studied on an enantiomeric level during a 148-day exposure experiment. Chiral separation and analysis of the two pairs of enantiomers were achieved using HPLC-MS/MS with a chiralpak IC chiral column. Benalaxyl decreased with half-life of 16.1 days in soil under tap water irrigation with preferential residue of S-benalaxyl. Benalaxyl acid was formed with great preference of R-enantiomer before 21 days while enriched in S-enantiomer afterwards. The degradation of benalaxyl was restrained by both wastewater and treated wastewater irrigation, but the enantioselectivity in S-benalaxyl residue was enhanced. Benalaxyl acid was also formed with similar enantioselectivity as in tap water irrigation. Sewage sludge could accelerate benalaxyl degradation with shorter half-life. Surprisingly, the enantioselectivity with preference degradation of S-enantiomer in sewage sludge was opposite to that in soil. More benalaxyl acid was generated with EF values always lower than 0.5 and remained longer in sewage sludge than in soil. A sterilization experiment indicated that the conversion of benalaxyl to benalaxyl acid and the enantioselectivity were determined by the microorganisms in soil or sewage sludge. Farming practices like wastewater irrigation and sewage sludge application might not only influence the fate of pesticide, but also the enantioselectivity of chiral pesticide enantiomers and thus the risks of pesticide residues posed to the environment.

Trace elements are added to poultry feed to control infection and improve weight gain. However, the fate of these trace elements in poultry litter is poorly understood. Because poultry litter is applied as fertilizer in many agricultural regions, evaluation of the environmental processes that influence the mobility of litter-derived trace elements is critical for predicting if trace elements are retained in soil or released to water. This study examined the effect of dissolved organic carbon (DOC) in poultry litter leachate on the fate and transport of litter-derived elements (As, Cu, P and Zn) using laboratory column experiments with soil collected from the Delmarva Peninsula (Mid-Atlantic, USA), a region of intense poultry production. Results of the experiments showed that DOC enhanced the mobility of all of the studied elements. However, despite the increased mobility, 60–70% of Zn, As and P mass was retained within the soil. In contrast, almost all of the Cu was mobilized in the litter leachate experiments, with very little retention in soil. Overall, our results demonstrate that the mobility of As, Cu, Zn and P in soils which receive poultry litter application is strongly influenced by both litter leachate composition, specifically organic acids, and adsorption to soil. Results have implications for understanding fate and transport of trace elements released from litter application to soil water and groundwater, which can affect both human health and the environment.

The Long-Term Sludge Experiments (LTSE) began in 1994 as part of continuing research into the effects of sludge-borne heavy metals on soil fertility. The long-term effects of Zn, Cu, and Cd on soil microbial biomass carbon (Cmic) were monitored for 8 years (1997-2005) in sludge amended soils at nine UK field sites. To assess the statutory limits set by the UK Sludge (Use in Agriculture) Regulations the experimental data has been reviewed using the statistical methods of meta-analysis. Previous LTSE studies have focused predominantly on statistical significance rather than effect size, whereas meta-analysis focuses on the magnitude and direction of an effect, i.e. the practical significance, rather than its statistical significance. The results presented here show that significant decreases in Cmic have occurred in soils where the total concentrations of Zn and Cu fall below the current UK statutory limits. For soils receiving sewage sludge predominantly contaminated with Zn, decreases of approximately 7–11% were observed at concentrations below the UK statutory limit. The effect of Zn appeared to increase over time, with increasingly greater decreases in Cmic observed over a period of 8 years. This may be due to an interactive effect between Zn and confounding Cu contamination which has augmented the bioavailability of these metals over time. Similar decreases (7–12%) in Cmic were observed in soils receiving sewage sludge predominantly contaminated with Cu; however, Cmic appeared to show signs of recovery after a period of 6 years. Application of sewage sludge predominantly contaminated with Cd appeared to have no effect on Cmic at concentrations below the current UK statutory limit.