The problem of potentially toxic elements (PTEs) in farmland is a key issue in global pollution prevention and control and has an important impact on environmental safety, human health, and sustainable agricultural development. Based on the climate background of high–latitude cold regions, this study simulated freeze–thaw cycles through indoor tests. Different initial conditions, such as biochar application rates (0%, 1%, 2%) and different initial soil moisture contents (15%, 20%, 25%), were set to explore the morphological changes in cadmium (Cd) and lead (Pb) in soil and the response relationship to the changes in soil physicochemical properties. The results indicate that soil pH decreases during freeze–thaw cycles, and soil alkalinity increases with increasing biochar content. Freeze–thaw cycles caused the total amount of PTEs to have a U–shaped distribution, and the amount of PTEs in the soluble (SOL) and reducible (RED) fraction increased by 0.28–56.19%. Biochar reduced the amount of Cd and Pb migration in the soil, and an increase in soil moisture content reduced the availability of Cd and Pb in the soil. Freezing and thawing damaged the soil structure, and biochar reduced the fractionation of small particle aggregates by enhancing the stability of soil aggregates, thereby reducing the soil's ability to adsorb Cd and Pb. In summary, for farmland soil remediation and pollution control, the application of biochar has a certain ability to optimize soil properties. Considering the distribution of PTEs in the soil and the physicochemical properties of the soil, the application of 1% biochar to soil with a 20% moisture content is optimal for regulating seasonally frozen soil remediation.

In peri-urban critical zones, soil ecosystems are highly affected by increasing urbanization, causing probably an intense interaction between dissolved organic matter (DOM) and heavy metals in soil. Such interaction is critical for understanding the biogeochemical cycles of both organic matter and heavy metals in these zones. However, limited research has reported the correlative distribution of DOM and heavy metals at high seasonal and spatial resolutions in peri-urban critical zones. In this study, 160 soil samples were collected from the farmland and forestland of Zhangxi watershed, in Ningbo, eastern China during spring, summer, fall and winter four seasons. UV–visible absorption and fluorescent spectroscopy were used to explore the optical characteristics of DOM. The results indicated a mixture of exogenous and autogenous sources of DOM in the Zhangxi watershed, while DOM in farmland exhibited a higher degree of aromaticity and humification than that in forestland. Fluorescent results showed that humic acid-like, fulvic acid-like and microbial-derived humic-like fractions were mostly affected by seasons. The distribution of heavy metals was affected mainly by land-use changes and seasons. Correlation analysis between heavy metals and DOM characteristics and components suggested that aromatic and humic substances were more favorable in binding with EDTA extractable Ni, Cu, Zn and Cd. The bioavailable Cd and Pb decreased due to binding with humic fractions, indicating its great effects on the bioavailability of Cd and Pb. Overall, these findings provide an insight into the correlative distributions of DOM and heavy metals in peri-urban areas, thereby highlighting their biogeochemical cycling in the soil environment.

Optimizing landscape pattern to reduce the risk of non-point source (NPS) pollution is an effective measure to improve river water quality. The “source-sink” landscape theory is a recent research tool for landscape pattern analysis that can effectively integrate landscape type, area, spatial location, and topographic features to depict the spatial heterogeneity of NPS pollution. Based on this theory, we quantitatively analyzed the influence of “source-sink” landscape pattern on the river water quality in one of the most intensive agricultural watersheds in Southeastern China. The results indicated that the proportion of “sink” landscape (68.59%) was greater than that of “source” landscape (31.41%) in the study area. In addition, when elevation and slope increased, the “source” landscape proportion decreased, and the “sink” landscape proportion increased. Nitrogen (N) and phosphorus (P) pollutants in rivers showed significant seasonal and spatial variations. Farmland was the primary source of nitrate nitrogen (NO₃⁻-N) and total nitrogen (TN) pollution, whereas residential land was the primary source of ammonium nitrogen (NH₄⁺-N) and total phosphorus (TP) pollution. Intensively cultivated areas and densely inhabited areas degraded water quality despite high proportions of forest land. The four “source-sink” landscape indices (LWLI, LWLI'e, LWLI's, LWLI'd) had significant positive correlations with NO₃⁻-N and TN and weak correlations with NH₄⁺-N and TP. The capacity of LWLI to quantify the NPS pollution was greater in agricultural areas than in residential areas. The “source-sink” landscape thresholds resulted in abrupt changes in water quality. When LWLI was ∼0.35, the probability of river water quality degradation increased sharply. The results suggest the importance of optimizing the “source-sink” landscape pattern for mitigating agricultural NPS pollution and provide policy makers with adequate new information on the agroecosystem-environmental interface in highly developed agricultural watersheds.

Conservation agriculture through no-till based on cropping systems with high biomass-C input, is a strategy to restoring the carbon (C) lost from natural capital by conversion to agricultural land. We hypothesize that cropping systems based on quantity, diversity and frequency of biomass-C input above soil C dynamic equilibrium level can recover the natural capital. The objectives of this study were to: i) assess the C-budget of land use change for two contrasting climatic environments, ii) estimate the C turnover time of the natural capital through no-till cropping systems, and iii) determine the C pathway since soil under native vegetation to no-till cropping systems. In a subtropical and tropical environment, three types of land use were used: a) undisturbed soil under native vegetation as the reference of pristine level; b) degraded soil through continuous tillage; and c) soil under continuous no-till cropping system with high biomass-C input. At the subtropical environment, the soil under continuous tillage caused loss of 25.4 Mg C ha⁻¹ in the 0–40 cm layer over 29 years. Of this, 17 Mg C ha⁻¹ was transferred into the 40–100 cm layers, resulting in the net negative C balance for 0–100 cm layer of 8.4 Mg C ha⁻¹ with an environmental cost of USD 1968 ha⁻¹. The 0.59 Mg C ha⁻¹ yr⁻¹ sequestration rate by no-till cropping system promote the C turnover time (soil and vegetation) of 77 years. For tropical environment, the soil C losses reached 27.0 Mg C ha⁻¹ in the 0–100 cm layer over 8 years, with the environmental cost of USD 6155 ha⁻¹, and the natural capital turnover time through C sequestration rate of 2.15 Mg C ha⁻¹ yr⁻¹ was 49 years. The results indicated that the particulate organic C and mineral associate organic C fractions are the indicators of losses and restoration of C and leading C pathway to recover natural capital through no-till cropping systems.

Nitrogen loss via overland flow from agricultural land use is a global threat to waterways. On-farm denitrifying woodchip bioreactors can mitigate NO₃⁻ exports by increasing denitrification capacity. However, denitrification in sub-optimal conditions releases the greenhouse gas nitrous oxide (N₂O), swapping the pollution from aquatic to atmospheric reservoirs. Here, we assess NO₃⁻-N removal and N₂O emissions from a new edge-of-field surface-flow bioreactor during ten rain events on intensive farming land. Nitrate removal rates (NRR) varied between 5.4 and 76.2 g NO₃⁻-N m⁻³ wetted woodchip d⁻¹ with a mean of 30.3 ± 7.3 g NO₃⁻-N m⁻³. The nitrate removal efficiency (NRE) was ∼73% in ideal hydrological conditions and ∼18% in non-ideal conditions. The fraction of NO₃⁻-N converted to N₂O (rN₂O) in the bioreactor was ∼3.3 fold lower than the expected 0.75% IPCC emission factor. We update the global bioreactor estimated Q₁₀ (NRR increase every 10 °C) from a recent meta-analysis with previously unavailable data to >20 °C, yielding a new global Q₁₀ factor of 3.1. Mean N₂O CO₂-eq emissions (431.9 ± 125.4 g CO₂-eq emissions day⁻¹) indicate that the bioreactor was not significantly swapping aquatic NO₃⁻ for N₂O pollution. Our estimated NO₃⁻-N removal from the bioreactor (9.9 kg NO₃⁻-N ha⁻¹ yr⁻¹) costs US$13.14 per kg NO₃⁻-N removed and represents ∼30% NO₃⁻-N removal when incorporating all flow and overflow events. Overall, edge-of-field surface-flow bioreactors seem to be a cost-effective solution to reduce NO₃⁻-N runoff with minor pollution swapping to N₂O.

Wastewater treatment plants (WwTPs) remove microplastics (MPs) from municipal sewage flow, with the resulting bulk of MPs being concentrated within generated sewage sludge which is frequently recycled back onto agricultural land as accepted practice in many European countries as a sustainable fertiliser resource. This circular process means that MPs successfully removed from WwTPs are deposited into the soil and able to return into the natural watercourse by means of run-off or infiltration to groundwater. This study quantifies the removal efficiency of MPs with size ranging between 1000 and 5000 μm in a primary settlement tank (PST) at a WwTP serving a population equivalent of 300,000 and provides MP concentrations in the generated sewage sludge. Our study revealed that the proportion of MPs partitioning in a PST to settled sludge, floating scum and effluent was 96%, 4% and 0% respectively, implying 100% removal of MPs of 1000–5000 μm in size. The generated sewage sludge was estimated to contain concentrations of approximately 0.01 g of MPs or 24.7 MP particles per g of dry sewage sludge solid, equivalent to ∼1% of the sewage sludge weight. Using these figures and data from the European Commission and Eurostat, the potential yearly MP contamination onto soils throughout European nations is estimated to be equivalent to a mass of MPs ranging between 31,000 and 42,000 tonnes (considering MPs 1000–5000 μm in size) or 8.6×10¹³–7.1×10¹⁴ MP particles (considering MPs 25–5000 μm in size). An estimated maximum application rate of 4.8 g of MP/m²/yr or 11,489 MP particles/m²/yr, suggests that the practice of spreading sludge on agricultural land could potentially make them one of the largest global reservoirs of MP pollution. Hence, recycling raw sewage sludge onto agricultural soils should be reviewed to avoid introducing extreme MP pollution into the environment.

Mulch film (MF) residues is an important source of microplastics (MPs) in farmland, but its transportation risk to the wider environment was still unknown. Some researches have pursued the sources of MPs found in exorheic rivers. Even so, a systematic study depicting the occurrence, source and fate of microplastics derived from mulch films (MPMF), the crucial component of MPs in farmlands, in exorheic rivers still lacking. Here, the combination of UV–Vis Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) was used to identify the full-size MPMF (1–5000 μm) in field sediment samples collected by single-diagonal systematic sampling. This study verified that MPMF, a polyethylene-matrix composite doped with additives, contributed a considerable part of MPs detected in upstream farmland soil and riverine sediments, and even had an abundance of 38 ± 11 items/kg to 82 ± 15 items/kg, accounting for 9.0%–13.7% of the total MPs in estuary sediments. Notably, upstream farmland was identified to the main source of the riverine MPMF by partial least square path modeling (PLS-PM), contributing to 94.7% of MPMF in riverside sediments and 85.0% of MPMF in estuary sediments. Our study first demonstrates that MPMF constitutes a non-negligible component of MPs in estuarine sediments and underlines the urgency of strengthening the management of MPs pollution in drainage areas with a high agricultural intensity.

Plastic film mulch (PFM) is a double-edged-sword agricultural technology, which greatly improves global agricultural production but can also cause severe plastic pollution of the environment. Here, we characterized and quantified the amount of macro- and micro-plastics accumulated after 32 years of continuous plastic mulch film use in an agricultural field. An interactive field trial was established in 1987, where the effect of plastic mulching and N fertilization on maize yield was investigated. We assessed the abundance and type of macroplastics (>5 mm) at 0–20 cm soil depth and microplastic (<5 mm) at 0–100 cm depth. In the PFM plot, we found about 10 times more macroplastic particles in the fertilized plots than in the non-fertilized plots (6796 vs 653 pieces/m²), and the amount of film microplastics was about twice as abundant in the fertilized plots than in the non-fertilized plots (3.7 × 10⁶ vs 2.2 × 10⁶ particles/kg soil). These differences can be explained by entanglement of plastics with plant roots and stems, which made it more difficult to remove plastic film after harvest. Macroplastics consisted mainly of films, while microplastics consisted of films, fibers, and granules, with the films being identified as polyethylene originating from the plastic mulch films. Plastic mulch films contributed 33%–56% to the total microplastics in 0–100 cm depth. The total number of microplastics in the topsoil (0–10 cm) ranged as 7183–10,586 particles/kg, with an average of 8885 particles/kg. In the deep subsoil (80–100 cm) the plastic concentration ranged as 2268–3529 particles/kg, with an average of 2899 particles/kg. Long-term use of plastic mulch films caused considerable pollution of not only surface, but also subsurface soil. Migration of plastic to deeper soil layers makes removal and remediation more difficult, implying that the plastic pollution legacy will remain in soil for centuries.

Scientific literature is full of works studying the removal of different pollutants from water through different Advanced Oxidation Processes (AOPs). Many of them only suggest it is reused for agricultural purposes or for small crops in pots. This study is based on the reuse of reclaimed agricultural wastewater contaminated with four insecticides (chlorantraniliprole, imidacloprid, pirimicarb and thiamethoxam) for growing lettuce in field conditions. First, solar photocatalysis with TiO₂/Na₂S₂O₈ was used on a pilot plant in a sunny area (Murcia, SE of Spain) as an environmentally friendly technology to remove insecticide residues and their main reaction intermediates from contaminated water. The necessary fluence (H, kJ m⁻²) to accomplish 90% removal (H₉₀) ranged from 0.12 to 1212 kJ m⁻² for pirimicarb and chlorantraniliprole, respectively. Only six (derived from imidacloprid, pirimicarb and thiametoxam) of 18 transformation intermediate products studied were detected in reclaimed water during the photoperiod (2000 kJ m⁻² of accumulated UVA radiation) although all of them were totally photodegraded after a fluence of 1250 kJ m⁻². Secondly, reclaimed agro-wastewater was used to irrigate two lettuce crops grown under greenhouse conditions and under agricultural field conditions. In no cases, insecticide residues nor their TIPs were noticed above their respective LOQs (limits of quantification) in soil and lettuce samples (between 0.03 and 0.04 μg kg⁻¹ for pirimicarb and 2.49 and 2.23 μg kg⁻¹ for thiamethoxam, respectively) when they were irrigated with reclaimed water, while residues of the four insecticides and some of their intermediates were found in soil and lettuce by the end of cultivation when they were irrigated with non-reclaimed contaminated water. According to the results, this technology can be applied in a sustainable way, mainly in areas with water scarcity and high solar radiation, contributing to water utilisation in drought areas and the use of renewable energy.

Identifying the bioavailability and release-desorption mechanism of heavy metals (HMs) in soil is critical to understand the release risk of HMs. Simultaneously, the mechanistic investigation of affecting the bioavailability of HMs in soil is necessary, such as the grain-size distribution and soil mineralogy. Herein, the bioavailability of HMs (Cu, Cd, Ni, Pb, and Zn) in different area soils near a typical copper-smelter was evaluated by the sequential extraction technique (BCR), diffusive gradients in thin-films (DGT), and DGT-induced fluxes in sediments (DIFS) model. Results showed that the HMs proportion of the residual fraction in all soils was the highest. The average bioavailability concentration (CDGT) of Cu and Cd in industrial soil was the highest, with 45.12 μg· L⁻¹ and 9.06 μg· L⁻¹. The result of DIFS model revealed that the decreased order of the mean value of desorption rate constant (K₋₁) was Cd > Zn > Ni > Cu > Pb, 5.91 × 10⁻⁵, 4.96 × 10⁻⁵, 2.89 × 10⁻⁵, 9.64 × 10⁻⁶, and 8.69 × 10⁻⁶, respectively. According to the spatial distribution of release potential (R-value), the release potential of labile-Cu in agricultural soil was the highest, which was mainly attributed to fertilizer application in farmland. Simultaneously, the reduced hydroxyl was also related to the agricultural activities, resulting in the weakened adsorption capacity of HMs by soil. Redundancy analysis (RDA) results showed that the bioavailability of Cd, Ni, and Zn was mainly driven by soil pH, while the bioavailability of Cu and Pb was primarily driven by dissolved organic carbon (DOC). Meanwhile, carbonate minerals had a positive correlation with the bioavailability of Cd, Ni, and Zn, which could promote the release of HMs in mining soil as chemical weathering progresses. In conclusion, this study provides a structured method which can be used as a standard approach for similar scenarios to determine the geochemical fractionation, bioavailability, and release kinetics of heavy metals in soils.