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.

Veterinary antibiotics have been detected as contaminants of emerging concern in soil environment worldwide. Animal manure is frequently applied to agricultural fields to improve soil fertility, which can result in introducing large amount of antibiotics into soil environment. However, few attempts have been made to identify the spatial and temporal dynamics of veterinary antibiotics in soil at the hillslope scale with different land uses. This study was performed to explore the pattern and variability of veterinary antibiotics in the soil in response to rainfall events. Results showed that higher concentrations of veterinary antibiotics were generally found in cropland (292.6 ± 280.1 ng/g) and orchard (228.1 ± 230.5 ng/g) than in forestland (13.5 ± 9.9 ng/g). After rainfall events, antibiotics accumulated in the soil at the positions where manure was applied, especially under high-intensity rainfall conditions. However, the antibiotic concentration in soil slightly increased from the top to the bottom of hills, thus indicating the restricted contribution of runoff to antibiotic transport, especially under low-intensity rainfall conditions. In addition, most antibiotics were sequestered in the surface soil (0–10 cm), and higher antibiotic concentrations were observed in deep soil (20–40 cm) in cropland than orchard. The soil aggregate, organic matter, and clay content played important roles in antibiotic sequestration along the hillslope subject to low-, medium-, and large-amount rainfall events, respectively. This study identified that land use, rainfall conditions, and soil structures jointly affect the spatial and temporal variability of antibiotics in soils on hillslopes.

Organophosphate esters (OPEs) pose increasing concerns for their widespread distribution in soil environments and potential threat to human health. In this study, we investigated the occurrence and associated risks of seven OPEs in surface soils and the potential influence of human activities on soil OPE contamination in a heavily urbanized region of the Yangtze River Delta in Eastern China. All target OPEs were detected in the soil samples (100% of samples) reflecting their widespread distribution in the study region. The total OPE concentration (the sum of the seven OPEs) ranged from 162.7 to 986.0 ng/g on a dry weight basis, with a mean value of 469.3 ± 178.6 ng/g. Tris (2-butoxyethyl) phosphate was the main compound, accounting for 67–78% of the total OPE concentration. Ecological risk assessment showed that tris(2-chloroisopropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(2-butoxyethyl) phosphate, and tris(2-ethylhexyl) phosphate posed a medium potential risk to terrestrial biota (0.1 < risk quotient <1). The human exposure estimation showed insignificant risks to local population. Redundancy analysis revealed that the individual and total OPE contaminations were positively correlated with human activity parameters. The total OPE concentrations were positively correlated to population density (R² = 0.38, P < 0.001), and urban land use percentage (R² = 0.39, P < 0.001), while negatively correlated to forest land use percentage (R² = 0.59, P < 0.001), suggesting a significant contribution of human disturbance to OPE pollution. These results can facilitate OPE contamination control and promote sustainable soil management in urbanized and industrialized regions.

Nitrogen (N) is an essential nutrient but may become a pollution source in the environment when the N concentration exceeds a certain threshold for humans and nature. Nitrate is a major N species in river water with notable spatial and temporal variations under the influences of natural factors and anthropogenic N inputs. We analyzed the relationship between riverine N (focusing on nitrate) concentration and various factors (land use, climate, basin topography, atmospheric N deposition, agricultural N sources and human-derived N) in 104 rivers located throughout the Japanese Archipelago except small remote islands. We aimed to better understand processes and mechanisms to explain the spatial and temporal changes in riverine nitrate concentration. A publicly available river water quality database observed in the 1980s (1980–1989) and 2000s (2000–2009) was used. This study is the first to evaluate the long-term scale of 20 years in the latter half of Japan's economic growth period at the national level. A geographic information system (GIS) was employed to determine average values of each variable collected from multiple sources of statistical data. We then performed regression analysis and structural equation modeling (SEM) for each period. The forestland area influenced by the basin topography, climate (i.e., air temperature) and other land uses (i.e., farmland and urban area) played a major role in decreasing nitrate concentrations in both the 1980s and 2000s. Atmospheric N deposition (especially N oxides) and agricultural N sources (fertilizer and manure) were also significant variables regarding the spatial variations in riverine nitrate concentrations. The SEM results suggested that human-derived N (via food consumption) intensified by demographic shifts during the 2000s increased riverine nitrate concentrations over other variables within the context of spatial variation. These findings facilitate better decision making regarding land use, agricultural practices, pollution control and individual behaviors toward a sustainable society.

Heavy metals in atmospheric dust can directly pollute the soil, water and sediment, causing serious harm to human health. In this study, the temporal and spatial distribution characteristics of heavy metals in atmospheric deposition in western Taihu Lake were studied. We established 10 sampling sites to collect atmospheric deposition for two years in different seasons. The atmospheric deposition flux follows the order urban area (95.6 g m⁻²·a⁻¹) > suburban area (80.2 g m⁻²·a⁻¹) > forestland (56.8 g m⁻²·a⁻¹). The concentrations of heavy metals in atmospheric deposition show trends of high values in the winter and low values in the summer and are significantly negatively correlated with distance from the city. The pollution level of Igₑₒ-Cd is 6, which is very high, and that of E-Cd is 219, which means high risk. Heavy metals in atmospheric deposition are mainly taken up via hand-mouth intake, and the harm to children is significantly higher than the harm to adults. The highest health risk assessment values for the four analyzed heavy metals in atmospheric deposition are located near the city and in suburbs (within 5 km of the city center), that is, in areas where human activities are concentrated. The health risk assessment values in areas outside the suburbs are low; these areas are less affected by human activities. The health risk assessment values of heavy metals in the winter and spring are higher than those in the summer and autumn. The Pb isotope ratios show that the main sources of heavy metals in atmospheric deposition and local soil are human activities, such as industry and coal combustion, with less input from natural sources. Heavy metals in atmospheric deposition in the western part of Taihu Lake not only directly threaten local human health but also enter Taihu Lake, posing a serious threat to the Taihu Lake ecosystem.

Riparian areas are widely recognized as the main areas for carbon sequestration and nitrogen pollution removal, while little is known about the effects of the respective sand mining activities on riparian zones. In this study, the effects of sand mining activities on the soil organic carbon (SOC) storage, different N-removal processes (Feammox, anammox, and denitrification), and composition of the relative bacterial community at a depth of 0–40 cm were determined based on investigations in riparian sand mining areas and adjacent forestlands. The SOC density of the sand mining areas (2.59 t ha⁻¹, depth of 0–40 cm) was lower than that of the riparian forestlands (80.42 t ha⁻¹). Compared with those of the riparian forestland, the sand mining area exhibited a dramatic reduction in the CO₂-fixed gene abundances (cbbL) and a significant change in the composition of cbbL-containing bacteria. The rates of the Feammox (0.038 ± 0.014 mg N kg⁻¹ d⁻¹), anammox (0.017 ± 0.017 mg N kg⁻¹ d⁻¹), and denitrification (0.090 ± 0.1 mg N kg⁻¹ d⁻¹) processes at a depth of 0–20 cm in the soil layer of the sand mining area were reduced by 70.17%, 91.5%, and 93.62% compared with those of the riparian forestland, respectively. The riparian areas in the study area (approximately 12 ha, depth of 0–40 cm) destroyed by sand mining activities released approximately 933.96 t stored soil carbon, which reduce the annual carbon sequestration potential by 28.8–40.8 t. Moreover, the potential N-removal rates in the riparian forestlands (depth of 0–20 cm) by the Feammox, anammox, and denitrification processes were 1514.21–1530.95 kg N ha⁻¹ year⁻¹, whereas the potential N-removal rates in the sand mining area were only 121.2–126.19 kg N ha⁻¹ year⁻¹. Therefore, more investigations are necessary for comparing the benefits and damage of sand mining activities in riparian areas before more sand mining activities are approved.

The occurrence and spatial distribution of selected pesticides were investigated along a 200-km reach of the St. Lawrence River (SLR) and tributaries in Quebec, Canada. Surface water samples (n = 68) were collected in the summer 2017 and analyzed for glyphosate, atrazine (ATZ), 8 systemic insecticides (acetamiprid, clothianidin, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam) and some metabolites. Overall, 99% of the surface water samples were positive to at least one of the targeted pesticides. The most recurrent compounds were glyphosate (detection frequency: 84%), ATZ (82%), thiamethoxam (59%), desethylatrazine (DEA: 47%), and clothianidin (46%). Glyphosate displayed variable levels (4–3,000 ng L−1), with higher concentrations in south tributaries (e.g., Nicolet and Yamaska). In positive samples, the sum of ATZ and DEA varied between 5 and 860 ng L−1, and the sum of 6 priority neonicotinoids between 1.5 and 115 ng L−1. From Repentigny to the Sorel Islands, the spatial distribution of pesticides within the St. Lawrence River was governed by the different upstream sources (i.e., Great Lakes vs. Ottawa River) due to the limited mixing of the different water masses. Cross-sectional patterns revealed higher concentrations of glyphosate and neonicotinoids in the north portions of transects, while the middle and south portions showed higher levels of atrazine. In Lake St. Pierre and further downstream, cross-sections revealed higher levels of the targeted pesticides near the southern portions of the SLR. This may be due to the higher contributions from south shore tributaries impacted by major agricultural areas, compared to north shore tributaries with forest land and less cropland use. Surface water samples were compliant with guidelines for the protection of aquatic life (chronic effects) for glyphosate and atrazine. However, 31% of the samples were found to surpass the guideline value of 8.3 ng L−1 for the sum of six priority neonicotinoids.

Increasing riverine phosphorus (P) levels in headwaters due to expanded and intensified human activities are worldwide concerns, because P is a well-known limiting nutrient for freshwater eutrophication. Here we adopt the conceptual framework of the SPAtially Referenced Regressions On Watershed attributes (SPARROW) model to describe total phosphorus (TP) sources and transport in a headwater watershed undergoing rapid agricultural expansion in the upper Taihu Lake Basin, China. Our models, which include variables for land cover, river length, runoff depth, and pond density, explain 94% of the spatio-temporal variability in TP loads. Agricultural lands contribute the largest percentage (61%) of the TP loads delivered downstream, followed by forestland (21%) and urban land (18%). Future agricultural expansion to 15% of the total basin area is possible, which could lead to a 50% increase in TP loads. According to our analysis, an average of 24% of the total P export from the watershed landscape was intercepted in ponds. The exported amount was subsequently retained by tributaries and along the mainstem river, accounting for 14% and 43% of their inflowing loads, respectively. The remaining ∼6 tons yr⁻¹ of TP was eventually transported into Tianmu Lake, in Southeastern China. The model identified several sub-catchments as hotspots of TP loss and thus logical sites for targeted management. Our study underscores the significance of agricultural expansion as a factor that can exacerbate headwater TP pollution, highlighting the importance of landscapes to buffer TP losses from sensitive hilly catchments. This also points to a need for an integrated management strategy that considers the spatial-varying P sources and associated transport of TP in precious headwater resources.

International audience | Zinc (Zn) and lead (Pb) concentrations were measured in 173 samples collected in soils under forest, wetland, and arable land around a Zn smelter plant that stopped activity in the 1960s. The adopted sampling strategy consisted in collecting 0–30-cm-depth samples from all soils, tilled or not, in order to harmonize the analyzed soil volume to that of plowed soils. Airborne deposition was modeled as a function of the distance from the pollution source and of land use. The Zn/Pb concentration ratios in the surface layer remarkably contrasted 3–4, 1.5–2, and ~ 0.5 for arable, wetland, and forest soils, respectively, independently from the distance to the emission source, while total Zn and Pb concentrations, taken separately, were only slightly discriminant. For metal pollution sites originating from former industrial activity, Zn/Pb concentration ratios determined on relevant soil samples represent a powerful indicator that provides easy and rapid information in real field conditions on time-related input/output dynamics of mobile and less-mobile metal pollutants, and hence, on interactions between pollutants and soils under different land use conditions.