Next to the city of Huelva (SW of Spain), around 100 Mt of phosphogypsum (PG) are stored in stacks on the salt-marshes of the Tinto River estuary covering a surface of about 1000 ha. Due to the high content of ²³⁸U series natural radionuclides of the PG, its acidic nature (pH about 3), and the fact that PG stacks were disposed without any kind of isolation from the substrate, they could produce a potential radioactive impact into the underlying sediments.The aim of this work is to assess the pollution of the underlying sediments by natural radionuclides coming from the PG stacks. To this end, seven cores were taken, and PG and sediments samples collected at different depths were analysed. The activity concentrations of the main long half-live natural radionuclides of interest were determined by applying both gamma-ray and alpha-particle spectrometry radiometric techniques.The results of this study showed that the first decimeters of salt-marsh sediment act as a “barrier” for the radionuclides coming from the PG stacks decreasing rapidly its activity concentration in depth, affecting mainly sediments located in the first 20 cm below the contact due to mixing processes. While ²³⁰Th, ²²⁶Ra and ²¹⁰Pb pollution is mainly restricted to the first 20 cm of sediments, U-isotopes can reach higher depths (up to around 50 cm) by leaching processes due to their lower reactivity and higher concentration in the polluted leachates. The obtained results have high relevance for the design of the perimeter channel which is projected to build in the restoration project, suggesting that should has around 1 m deep under the base of the PG stacks, to ensure the full collection of polluting leachates, and to prevent their release into the estuary of the Tinto River.

Current swine industry practice is to house animals in confinement facilities which capture and store feces and urine as slurry in pits below the production area. Additives and disinfectants may be introduced into the manure pits. This study was conducted to measure the effects of additives and disinfectants on temporal changes in swine slurry characteristics. Slurry from a commercial swine production facility in southeast Nebraska, USA was collected and transferred to 57 L reactors located within a greenhouse. Selected additives and disinfectants were added to the reactors and physical properties, chemical characteristics, and antibiotic concentrations were monitored for 40 days. Concentrations of dry matter (DM), total nitrogen (TN), phosphorus pentoxide (P₂O₅), calcium (Ca), magnesium (Mg), zinc (Zn), iron (Fe), manganese (Mn), and copper (Cu) were significantly greater than the Control in each of the reactors containing additives. The reactors in which the additives MOC-7, More Than Manure®, Sludge Away, and Sulfi-Doxx were introduced had significantly greater values of chemical oxygen demand (COD), total volatile solids (TVS), total suspended solids (TSS), total solids (TS), dry matter (DM), TN, P₂O₅, Ca, Mg, Zn, Fe, Mn, Cu and chlortetracycline than the other additive treatments. Concentrations of TVS and TSS were significantly lower in the reactors containing Clorox® and Virkon™ than the other disinfectant treatments. The total dissolved solids (TDS) concentration of 26,500 mg L⁻¹ and pH value of 7.27 obtained for the reactors containing Tek-Trol were significantly greater than measurements obtained for the other treatments. Concentrations of chlortetracycline and tiamulin of 8840 and 28.8 ng g⁻¹, respectively, were significantly lower for the treatments containing Tek-Trol. The sodium (Na) concentration of 1070 mg L⁻¹ measured in the reactors containing Clorox® was significantly greater than values for the other disinfectant treatments. The introduction of selected additives and disinfectants may influence certain physical properties, chemical characteristics, and antibiotic concentrations of swine slurry.

Few studies specifically address the possible associations between multiple-metal exposures and liver damage among the occupational population. This study aimed to explore the cross-sectional relationships of plasma metals with liver function parameters. For 571 on-the-spot workers in the manganese-exposed workers healthy cohort (MEWHC), we determined liver function parameters: total bilirubin (TBILI), direct bilirubin (DBILI), indirect bilirubin (IBILI), alanine transaminase (ALT) and aspartate transaminase (AST). Total concentrations of 22 plasma metals were measured by ICP-MS. The LASSO (least absolute shrinkage and selection operator) penalized regression model was applied for selecting plasma metals independently associated with liver function parameters. Multiple linear regression analyses and restricted cubic spline (RCS) were utilized for identifying the exposure-response relationship of plasma metals with liver function parameters. After adjusting for covariates and selected metals, a 1-SD increase in log-10 transformed levels of iron was associated with increases in the levels of TBILI, DBILI and IBILI by 20.3%, 12.1% and 23.7%, respectively; similar increases in molybdenum for decreases in levels of TBILI, DBILI and IBILI by 6.1%, 2.6% and 8.3%, respectively. The effect of a 1-SD increase in plasma copper corresponded decreases of 3.2%, 3.4% and 5.0% in TBILI, AST and ALT levels, respectively. The spline analyses further clarified the non-linear relationships between plasma iron and bilirubin whilst negative linear relationships for plasma molybdenum and bilirubin. Plasma iron was positively whilst plasma molybdenum was negatively associated with increased serum bilirubin levels. Further studies are needed to validate these associations and uncover the underlying mechanisms.

Mercury (Hg) is a toxic and persistent pollutant and has long-term impacts on ecological systems and human health. Coal-fired power plants (CFPPs) are the main source of anthropogenic Hg emission, and the emitted atmospheric Hg is deposited to the surrounding environments which causes soil pollution. To assess the effects of atmospheric Hg from CFPPs in China on the temperate steppe, Hg contents in the topsoil and subsoil were analyzed for samples collected from 80 sites in central Inner Mongolia during 2012–2015. The average content of Hg in topsoil and subsoil were 14.9 ± 10.4 μg kg⁻¹ and 8.9 ± 5.8 μg kg⁻¹, respectively. The principal components analysis (PCA) indicated that the soil organic matter content and atmospheric deposition were the main factors determining soil Hg content in Inner Mongolia. We used the power plant impact factor (PPIF) to evaluate the impacts of the surrounding CFPPs. The PPIF results showed the most positive correlation with Hg content in topsoil at more than 400 km distances, indicating that the contribution of the long-range transport of Hg emitted from CFPPs is regional in scale. Considering the potential of Hg accumulation in soil, long-term and regional measurements of soil Hg and stricter emission-limit standards for power plants should be implemented to control soil Hg pollution in China.

Shortly after an atmospheric release, the interception of radionuclides by crop canopies represents the main uptake pathway leading to food chain contamination. The food chain models currently used in European emergency decision support systems require a large number of input parameters, which inevitably leads to high model complexity. In this study, we have established a new relationship for wet deposited radionuclides to simplify the current modelling approaches. This relationship is based on the hypothesis that the stage of plant development is the key factor governing the interception of radionuclides by crops having horizontally oriented leaves (planophile crops). The interception fraction (f) and the leaf area index normalized (fLAI) and mass normalized (fB) interception fractions were assessed for spinach (Spinacia oleracea) and radish (Raphanus sativus) at different stages of plant development and for different contamination treatments and plant densities. A database of 191 f values for Cs-137 and Th-229 was built and complemented with existing literature covering various radionuclides and crops with similar canopy structure. The overall f increased with the plant growth, while the reverse was observed for fB. The fLAI significantly decreased by doubling the contaminated rainfall deposited. Fitting a multiple linear regression to predict the f value as a function of the standing biomass (B), and the radionuclide form (anion and cation) led to a better estimation of the interception (R² = 81%) than the ECOSYS-87 model (R² = 35%). Hence, the simplified modelling approach here proposed seems to be a suitable risk assessment tool as fewer parameters will minimize the model complexity and facilitate the decision-making procedures in case of emergencies, when countermeasures need to be identified and implemented promptly.

Toxic metals have been linked to a range of adverse health effects in freshwater organisms. However, for higher vertebrates, there is little understanding of the large-scale drivers of exposure. We quantified toxic metal/semi-metal concentrations in a sentinel freshwater top predator, the Eurasian otter (Lutra lutra), across England and Wales, and determined how this varied with key natural and anthropogenic factors. We related liver concentrations in 278 otters that died between 2006 and 2017 to habitat biogeochemistry, proximity to point source contamination and to biological characteristics (length, sex, condition). Evidence for any positive association with putative anthropogenic sources (mining, human population, known discharges) was weak or lacking in nearly all cases, with the exception of a positive association between lead and human population density. Despite concerns that burgeoning use of nanosilver in consumer products might increase silver concentrations in waste waters, there was no increase over time. Spatial variation in soil/sediment pH, precipitation, and soil calcium oxide are indicated as significant predictors of metal concentrations in otters (higher cadmium and silver in areas with lower pH and higher rainfall, and higher chromium and lead in areas of lower calcium oxide). Liver chromium and nickel concentrations declined significantly over time (Cr 0.030 ± 1.2 to 0.015 ± 1.3 μg/g dry weight, Ni 0.0038 ± 1.2 to 0.00068 ± 1.5 μg/g, between 2006–2009 and 2014–2017), but other metals showed no temporal change. Biotic associations were important, with age related accumulation indicated for mercury and cadmium (as well as interactions with body condition). Our results suggest that larger-scale geochemical and hydrological processes are important in determining metal exposure in otters, and we provide an indication of risk factors that may be of relevance for freshwater vertebrates in other countries with well-developed water pollution management.

Harmful cyanobacterial blooms produce lethal toxins in many aquatic ecosystems experiencing eutrophication. This manuscript presents results on the effects of cyanotoxins on the aerobic microbial communities residing at the interface of sediments and water columns with the ammonia-oxidizing bacteria (AOB) as the model microbial community. Microcystin-LR (MC-LR), a heavily researched cyanotoxin variant, was used as the model cyanotoxin. To measure cyanotoxin influence on the activity of nitrifying microbial communities, an enriched culture of AOBs collected from an ongoing partial nitrification-nitritation reactor was examined for its exposure to 1, 5 and 10 μg/L of MC-LR. The nitritation kinetics experiment demonstrated MC-LR’s ability at 1, 5, and 10 μg/L concentrations to prevent ammonium oxidation with statistically significant differences in nitritation rates between the blanks and spiked samples (One-way ANOVA, p < 0.05). Significantly decreased dissolved oxygen (DO) consumption during oxygen update batch tests demonstrated toxin’s influence on AOB’s oxidizing capabilities when exposed to even lower concentrations of 0.75, 0.5, and 0.25 μg/L of MC-LR in a separate set of experiments. Based on competitive kinetics, the MC-LR inhibition coefficient-the concentration needed to produce half-maximum inhibition of the mixed community AOBs was determined to be 0.083 μg/L. The stress tests proved the recovery of nitritation to some extent at lower MC-LR concentrations (1 and 5 μg/L), but significant irreversible inhibition was recorded when the AOB population was exposed to 10 μg/L MC-LR. The comparisons of amoA gene expressions corresponded well with nitrifying kinetics. All concentrations of MC-LR spiking were determined to produce a discernible impact on the AOB nitritation rate by either destroying the bacterial cell or immediately inhibiting the amoA gene expression.

Steroid estrogen residues (SEs) in the soil have attracted growing attention because of their potential for endocrine disruption. Soil organic matter (SOM) and soil remediation agent-biochar, both have important influences on the fate of SEs in the soil environment. This study compared the adsorption of 17β-estradiol (E2) on wheat straw biochar (W-BC) and cow manure biochar (C-BC) with main SOM components including biomacromolecules (cellulose, collagen and lignin) and humic acids (HA). The impact of pyrolysis temperature (350 °C, 550 °C, and 700 °C) on the adsorption capacity of biochar and different concentrations NaClO oxidation on the adsorption capacity of HA were also investigated. The experimental results showed that the adsorption of E2 by biomolecules conformed to the linear isotherm (R² > 0.88), and the adsorption of E2 on biochars and HA were well described by the Langmuir and Freundlich isotherm (R² > 0.94). Meanwhile, the order of the E2 adsorption capacity of sorbents was W-BC > C-BC > HA > lignin > collagen > cellulose. The adsorption capacity of biochar and SOM for E2 increased with the enhancement of aromaticity and hydrophobicity and the reduction of polarity. In addition, the increase of pyrolysis temperature of biochars also promoted the adsorption capacity of E2, while oxidation treatment with NaClO reduced the adsorption capacity of HA to E2. These results deepened the understanding of the adsorption behaviour of E2 on SOM and biochar, and expanded the understanding of the behaviour of SEs in the soil environment.

Plastic, and especially microplastic, contamination of soils has become a novel research field. After the detection of microplastics in soils, spatial distribution and dynamics are still unknown. However, the potential risks associated with plastic particles in soils cannot be sufficiently assessed without knowledge about the spatial distribution of these anthropogenic materials. Based on a spatial research approach, including soil surveys, this study quantified the mesoplastic (MEP, > 5.0 mm) and coarse microplastics (CMP, 2.0–5.0 mm) content of twelve floodplain soils. At four transects in the catchment area of the Lahn river (Germany), soils down to a depth of 2 m were examined for plastic content for the first time. MEP and CMP were detected through visual examination after sample preprocessing and ATR-FTIR analyses. Average MEP and CMP concentrations range between 2.06 kg⁻¹ (±1.55 kg⁻¹) and 1.88 kg⁻¹ (±1.49 kg⁻¹) with maximal values of 5.37 MEP kg⁻¹ to 8.59 CMP kg⁻¹. Plastic particles are heterogeneously distributed in samples. Both plastic size classes occur more frequently in topsoils than in soil layers deeper than 30 cm. The maximal depth of CMP occurrence lies between 75 and 100 cm. Most common CMP polymer type was PE-LD, followed by PP and PA. MEP and CMP particles occur frequently at near channel sides and more often on riparian strips or grassland than on farmland. Vertical distribution of CMP indicates anthropogenic relocation in topsoils and additional deep displacement through natural processes like preferential flow paths or bioturbation. By comparing sedimentation rates of the river with the maximum age of plastic particles, sedimentation as a deposition process of plastic in floodplains becomes probable. From our findings, it can be concluded that an overall widespread but spatial heterogenous contamination occurs in floodplain soils. Additionally, a complex plastic source pattern seems to appear in floodplain areas.

The excessive application of manure has caused a high load of phosphorus (P) in the North China Plain. Having an understanding of how manure application affects soil P changes and its transport between different soil layers is crucial to reasonably apply manure P and reduce the associated loss. Based on our 28-year field experiments, the compositions and changes of P species and the risk of P loss under excessive manure treatments were investigated, i.e., no fertilizer (CK), mineral fertilizer NPK (NPK), NPK plus 22.5 t ha⁻¹ yr⁻¹ swine manure (LMNPK), and NPK plus 33.75 t ha⁻¹ yr⁻¹ swine manure (HMNPK). Manure application increased the content of orthophosphate and myo-inositol hexaphosphate (myo-IHP), especially the orthophosphate content exceeded 95%. The amount of orthophosphate in manure and the conversion of organic P to inorganic P in soil were the main reasons for the increased soil orthophosphate. Compared with NPK treatment, soil microbial biomass phosphorus and alkaline phosphatase activity in LMNPK and HMNPK treatments significantly increased. Compared with NPK treatment, a high manure application rate under HMNPK treatment could increase the abundance of organic P-mineralization gene phoD by 60.0% and decrease the abundance of inorganic P-solubilization gene pqqC by 45.9%. Due to the continuous additional manure application, soil P stocks significantly increased under LMNPK and HMNPK treatments. Furthermore, part of the P has been leached to the 60–80 cm soil layer. Segmented regression analysis indicated that CaCl₂–P increased sharply when Olsen-P was higher than 25.1 mg kg⁻¹, however the content of Olsen-P did not exceed this value until 10 years after consecutive excessive manure application. In order to improve soil P availability and decrease the risk of P loss, the manure application rate should vary over time based on soil physicochemical conditions, plants requirements, and P stocks from previous years.