Chemically oxidative removal of polycyclic aromatic hydrocarbons (PAHs) in soil is related to their occurrence state. Whether the heterogeneity of natural organic matter has an effect on the occurrence of PAHs in soil and, if there is an effect, on the oxidative removal efficiency of PAHs remains unknown. In this study, the removal efficiencies of 16 priority PAHs aged in humic acids (HAs) of different soil aggregate fractions by various oxidants were investigated by combining soil fractionation and microreaction experiments. Results showed that the accumulations of PAHs in particulate HA (P-HA) and microaggregate occluded HA (MO-HA) mainly occurred in the early period of the aging time frame. In contrast, PAH accumulation in non-aggregated silt and clay associated HA (NASCA-HA) was relatively slow and tended to saturate in the late period of the aging time frame. The cumulative contents of PAHs throughout the entire aging period in MO-HA and NASCA-HA were significantly greater than that in P-HA. The aged PAHs in P-HA and NASCA-HA exhibited the highest and lowest removal efficiencies, respectively. This ranking was mainly governed by the molecular size and polarity of HAs. Sodium persulfate and potassium permanganate had the highest removal efficiencies in total PAHs in HAs, with average efficiencies of 85.8% and 79.1%, respectively, in P-HA. Hydrogen peroxide had the lowest degradation efficiency in PAHs. In particular, the degradation efficiency of total PAHs in NASCA-HA was lowered to 31.0%. PAH congeners in HAs showed a large difference in oxidative removal efficiency. Low-ring PAH was more easily degraded than medium- and high-ring PAHs, and in most treatments, fluoranthene and pyrene in the medium ring and benzo[a]pyrene in the high ring demonstrated higher efficiencies than other PAHs with the same number of rings. Our findings are useful in promoting the accurate and green remediation of PAH-contaminated soils.

Microplastics (MPs), as a new type of environmental pollutant, pose a serious threat to soil ecosystems. The activities of soil extracellular enzymes produced by microorganisms are the potential sensitive indicators of soil quality. However, little is known about the response mechanism of enzyme activities toward MPs on a long-term scale. Moreover, information on differences in enzyme activities across different soil aggregates is lacking. In this study, 150 days of incubation experiments and soil aggregate fractionation were combined to investigate the influence of MPs on extracellular enzyme activities in soil. 28% concentration of polyethylene with size 100 μm was adopted in the treatments added with MPs. The results show that MPs inhibited enzyme activities through changing soil nutritional substrates and physicochemical properties or through adsorption. Moreover, MPs competed with soil microorganisms for physicochemical niches to reduce microbial activity and eventually, extracellular enzyme activity. Enzyme activities in different aggregate-size fractions responded differently to the MPs exposure. The catalase in the coarse particulate fraction and phenol oxidase and β-glucosidase in the micro-aggregate fraction exerted the greatest response. With comparison, urease, manganese peroxidase, and laccase activities showed the greatest responses in the non-aggregated silt and clay fraction. These observations are believed to stem from differences in the key factors determining the enzyme activities in different aggregate-size fractions.The inhibitory pathway of microplastics on activities of extracellular enzymes in soil varies significantly across different aggregate fractions.

Condensed organic matters (COM) with black carbon-like structures are considered as long-term carbon sinks because of their high stability. It is difficult to distinguish COM from general organic matter by conventional chemical analysis, thus the contribution by and interaction mechanisms of organo-mineral complexes in COM stabilization are unclear and generally neglected. Molecular markers related to black carbon-like structures, such as benzene polycarboxylic acids (BPCAs), are promising tools for the qualitative and quantitative analysis of COM. In this study, one natural soil and two cultivated soils with 25 y- or 55 y-tillage activities were collected and the distribution characteristics of BPCAs were detected. All the investigated soils showed similar BPCA distribution pattern, and over 60% of BPCAs were detected in clay fraction. The extractable BPCA contents were substantially increased after mineral removal. The ratios of BPCA contents before and after mineral removal indicate the extent of COM-mineral particle interactions, and our results suggested that up to 73% COM were protected by mineral particles, and more stronger interactions were noted on clay than on silt. The initial cultivation dramatically decreased COM-clay interactions, and this interaction was recovered only slowly after 55-y cultivation. Kaolinite and muscovite are important for COM protection. But a possible negative correlation between BPCAs and reactive iron oxides of the cultivated soils suggested that iron may promote COM degradation when disturbed by tillage activities. This study provided a new angle to study the stabilization of COM and emphasized the importance of organo-mineral complexes for COM stabilization.

Hard coal is the predominant energy source in Poland. The unavoidable consequence of coal combustion is the production of huge amounts of ash which can be concentrated in radionuclides. The ashes from coal combustion are utilized or stored and may affect the quality of the environment. Therefore, the estimation of radionuclides in hard coal and by-products is of crucial importance. The analyzed samples included ashes produced in ash furnaces, power plants and individual home furnaces operating in the Upper Silesian Industrial Region, Southern Poland, during the hard coal burning. This paper presents radioactivity concentrations of ²²⁸Ra, ²²⁶Ra and ⁴⁰K in hard coal, bottom and fly ash samples from Polish coal-fired power plants obtained during various technological coal combustion processes and generated in individual domestic furnaces, determined using the HPGe gamma spectrometry technique. The measurements of ²³⁴,²³⁸U concentrations were performed after sample preparation using alpha-particle spectrometer. The concentrations of the obtained radionuclides differ greatly in the fly and bottom ash samples. The lowest concentrations of ²²⁶Ra, ²²⁸Ra, ²³⁴U, ²³⁸U were observed in bottom ashes from the co-firing of hard coal and biomass in a fluidized-bed furnace, whereas the highest concentrations of ²²⁶Ra (163 ± 6 Bq/kg), ²²⁸Ra (100 ± 2 Bq/kg) isotopes were found in the ashes from individual household furnaces. This means that both the feed coal type and combustion techniques have a direct impact on the concentration of radionuclides in ash. Hard coal silt samples may be enriched in radionuclides and the radioactive equilibrium between ²²⁶Ra and ²³⁸U even in the case of coal is not always achieved. The concentrations of the analyzed isotopes in ashes are 5-7-fold higher than in feed coal. Given that combustion by-products are utilized as construction products, it should be noted that for some ash samples, the radiological hazard indices approach or exceed the maximum permitted levels.

Evaluating the effects of anthropogenic pressure on the marine environment is one of the focal objectives in identifying strategies for its use, conservation and restoration. In this paper, we assessed the effects of chemical pollutants, grain size and plastic litter on functional traits, biodiversity and biotic indices. The study was conducted on the benthic communities of three harbours in the central Mediterranean Sea: Malta, Augusta and Syracuse, subjected to different levels of anthropogenic stress (high, medium and low, respectively). Six traits were considered, subdivided into 22 categories: reproductive frequency, environmental position, mobility, life habit, feeding habit and bioturbation. Functional diversity indices analysed were: Functional Divergence, Quadratic Entropy, Functional Evenness and Functional Richness. To assess the trait responses to environmental gradients, we applied RLQ analysis, which considers simultaneously the relationship between three components: environmental data (R), species abundances (L) and species traits (Q). From our analyses, significant relationships (P-value = 0.0018 for permutation of samples, and P-value = 0.00027 for permutation of species) between functional traits and environmental data were highlighted. The trait categories significantly influenced by environmental variables were those representing feeding habits and mobility. In particular, the first category was influenced by chemical pollutants (organotin compounds and polycyclic aromatic hydrocarbons) and grain size (silt and sand), while the latter category was influenced only by chemical pollutants.Pearson correlations performed for functional vs biotic and diversity indices confirmed the validity of the chosen conceptual framework for harbour environments. Finally, linear models assessing the influence of stressors on functional parameters underlined the link between environmental data vs benthic and functional indices. Our results highlight the fact that functional trait analysis provides a useful and fast method for detecting in greater depth the effects of multiple stressors on functional diversity in marine ecosystems.

The Conwy estuary was evaluated for sediment quality. Microtox bioassay revealed 38 of 39 sites were non-toxic. Hg ranged from 0.001 to 0.153 μg kg⁻¹, mean 0.026 mg kg⁻¹, Σ16 PAH from 18 to 1578 μg kg⁻¹, mean 269 μg kg⁻¹, Σ22 PAH, 18 to 1871 μg kg⁻¹ mean to 312 μg kg⁻¹, two sites had high perylene relative to ΣPAH. Σ22PAH correlated positively with TOC, clay and silt (R² 0.89, 0.92, 0.90) and negatively with sand. Multivariate statistics, delineated four spatial (site) and five variable (measurements) clusters. Spatial clustering relates to sediment grain size, in response to hydrodynamic processes in estuary; fine (clay to silt) sized sediments exhibit the highest Hg and PAH content, because these components partitioned into the fine fraction. Comparison to national and international environmental standards suggests Hg and PAH content of Conwy sediments are unlikely to harm ecology or transfer up into the human food chain.

Ten surface sediments collected from Joanes River, Bahia, Brazil in rainy and drought periods in 2019 were evaluated according to the enrichment factor (EF), potential ecological risk index (RI), potential contamination index (PCI), pollution load index (PLI), and index of geoaccumulation (Igₑₒ). Initially the dry sediment was subjected to granulometric analysis and determination of the concentration of organic matter. Then, the samples were digested in HNO₃ and analyzed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) to determine the metals cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb) and zinc (Zn). Zn and Cu were classified in that order as the most contaminated elements in most sediment. Comparison of the total metal concentrations with the threshold (TELs) and probable (PELs) effect levels in sediment quality guidelines suggested a more worrisome situation for Zn (648.83–1415.90 μg g⁻¹; PELZₙ = 315 μg g⁻¹), of which concentrations were occasionally associated with adverse biological effects in four sediments, followed by Cu in five sediments during dry and rainy periods; while adverse effects were rarely associated with Cd, Cr, Ni, and Pb. In another evaluation, Cd, Cu, Cr, and Zn could be considered the most dangerous in the entire river, as they were classified in the high levels of contamination by the PCI, associated with serious adverse effects in most samples. In an assessment regarding the ecological risks in the study environment, the sediment samples remained below the limit established by the risk index (IR). The Zn presented moderately severe enrichment (6.78–11.83) in all the collection stations in the dry and rainy periods, followed by the Cd that presented moderate enrichment (2.23–4.17), whose values exceeded almost 1000 times the background at one site. Through the PCA it was possible to evidence the existing correlation between metals, organic matter, and silt and clay fraction. The results obtained in the PCA represented more than 80% of the variance between the data. The environmental risk assessment revealed a significant increase in the risk associated with metals during the rainy season. This is probably due to the greater supply of organic matter from the leaching of the margins.

In this study, light intensities of Aliivibrio fischeri obtained from soil suspension and its filtrate were compared using field soils contaminated with heavy metals. The soils collected from rice paddy and forest had different soil textures with either high or low silt/clay content. The correlation between soil toxicity and soil solution toxicity for A. fischeri showed a high linearity in sandy soils with the slope of 0.586 (determination coefficient; R² = 0.709). Meanwhile, a lower correlation in silty/clay soils with the slope of 0.154 (R² = 0.067) was observed. When a solid phase bioluminescence inhibition test is carried out using soil suspension with a high silt/clay content, a large amount of A. fischeri seems to adhere to microparticles and/or microaggregates. It may result in the change of light intensity (i.e., distorted toxicity test result) that could not be corrected by the modified basic solid phase test protocol, and thus the toxicity is likely to be overestimated. Such alteration in the light intensity could be partially overcome using a regression equation accounting for microbial loss by adhesion. With the correction for microbial adhesion, the correlation between soil toxicity and soil solution toxicity in the selected soil samples with high silt/clay contents increased from 0.182 (R² = 0.130) to 0.571 (R² = 0.602). It is expected that soil toxicity can be evaluated through the prediction of soil solution toxicity after the proper correction of microparticles effects.

Being known with its agricultural fertility, the soil of the Nile Valley of Egypt was subjected to degradation due to fast urbanization and increased industrial activities in recent years. The quality of the agricultural soil and associated radiological health hazards to farm workers in the Northeastern Nile Valley was assessed based on the trace metal analyses (Hg, Cd, Zn, Pb, Cu, Mn, and Fe) and natural radionuclide measurements (²³⁸U, ²²⁶Ra, ²³²Th, ⁴⁰K, and ²¹⁰Pb) of twenty soil samples. Results indicated that the agricultural soil has concentrations of trace elements below the soil world average. However, a significant enrichment in Cd and Cu content was observed in some soil sites. The enrichment in some trace elements contents, especially the Cd metal, was attributed to the effects of the natural and human factors, including the occurrence and distribution of silt and clay deposits, the extensive use of municipal wastewater and pesticide, the incineration of agricultural wastes, and the emission from bricks factories and mazut-fired thermal power plants around the area. The estimated contamination and ecologic risk indices revealed that some soils in the area are uncontaminated with trace elements; others are “moderately contaminated” soil to “contaminated.” Results from the radiological measurements revealed that the activity concentrations of the investigated radionuclides were also below the world median activities of soil. The total annual effective dose rates from the different exposure pathways were calculated. The estimated excess lifetime cancer risk values for farm workers were greatly higher than that of the soil world average. This implies a high probability of introducing cancer over the lifetime of farmers in the study area.

In this study, hexabromocyclododecane (HBCD) in riverine and estuarine sediments was investigated in Osaka, Japan. The mean total HBCD concentration detected in sediments ranged from < 0.50 to 130 ng g⁻¹ dry weight. This exceeded the ubiquitous HBCD contamination level found globally but was lower than that in areas affected by point sources, such as textile industries and expanded polystyrene plants. Sewage effluent was one of the suspected point sources of HBCD in the study area. The HBCD concentrations in sediments were highly dependent on certain factors, such as the location of the sampling site (proximity to possible emission sources), sediment properties (silt or sand), and organic substance content. The range of the diastereomer composition of α- and γ-HBCD was wider than that in other studies. Repeatability tests (n = 3) were conducted for all samples to assess the variability in the HBCD concentrations within identical sediment samples. Some variations were observed in the HBCD concentrations and diastereomer compositions within the repeatability test results at some sampling sites; nevertheless, the same samples were extracted and analyzed in triplicate. The bromine contents of the extracts of these samples were analyzed by X-ray fluorescence, and the results agreed well with those estimated from the LC-MS/MS results. From these results, it was confirmed that several sediment samples contained heterogeneously distributed HBCD. The risk characterization ratios (predicted environmental concentration/predicted no-effect concentration) of sites with high HBCD concentrations ranged from 0.1 to 1; thus, further information is required, and the sediment HBCD levels in this region should be continuously studied.