Chemical Fractionation Research Articles

Phosphorus speciation in manure and fertilizer impacted Mid-Atlantic coastal plain soils.

Historical applications of manures and fertilizers at rates exceeding crop P removal in the Mid-Atlantic region (United States) have resulted in decades of increased water quality degradation from P losses in agricultural runoff. As such, many growers in this region face restrictions on future P applications. An improved understanding of the fate, transformations, and availability of P is needed to manage P-enriched soils. We paired chemical extractions (i.e., Mehlich-3, water extractable P, and chemical fractionation) with nondestructive methods (i.e., x-ray absorption near edge structure [XANES] spectroscopy and x-ray fluorescence [XRF]) to investigate P dynamics in eight P-enriched Mid-Atlantic soils with various management histories. Chemical fractionation and XRF data were used to support XANES linear combination fits, allowing for identification of various Al, Ca, and Fe phosphates and P sorbed phases in soils amended with fertilizer, poultry litter, or dairy manure. Management history and P speciation were used to make qualitative comparisons between the eight legacy P soils; we also speculate about how P speciation may affect future management of these soils with and without additional P applications. With continued P applications, we expect an increase in semicrystalline Al and Fe-P, P sorbed to Al (hydro)oxides, and insoluble Ca-P species in these soils for all P sources. Under drawdown scenarios, we expect plant P uptake first from semicrystalline Al and Fe phosphates followed by P sorbed phases. Our results can help guide management decisions on coastal plain soils with a history of P application.

Tracking of uranium and thorium natural distribution in the chemical fractions of the Nile Valley and the Red Sea phosphorites, Egypt

The present study aims to elucidate the possible sources of uranium and thorium content in the Campanian–Maastrichtian phosphorites from the Duwi Formation in the Nile Valley and Red Sea by conducting facies analysis and sequential leaching method. Nile Valley samples were collected from the El-Sibaiya East area, while those of the Red Sea were collected from two locations: Hamadat and Zug El Bahar. The petrographic investigation revealed that the Sibaiya East phosphorites exhibit peloidal bioclastic phospharenite–phospharudite microfacies, while Hamadat and Zug El Bahar phosphorites display peloidal bioclastic phosphalutite and silicified peloidal bioclastic phospharenite microfacies, respectively. Besides, U–Th bearing accessory minerals, such as zircon and monazite occur in Sibaiya East phosphorites. Thorium is present in Zug El Bahar phosphorites as minute accumulations associating apatite and quartz. Moreover, uranium is found with vanadium and iron as fine patches in the Sibaiya East phosphorite, and as small disseminations associated with Ca and Si in the Hamadat phosphorite. The X-ray diffraction shows that the investigated phosphorites are essentially built up of hydroxyl apatite Ca5(PO4)3(OH) and quartz SiO2. To accurately evaluate the bioavailability and mobility of uranium and thorium in the investigated phosphorites, it was necessary to identify the overall concentration and the various chemical forms of these elements by a five-step sequential leaching technique. The results indicate that Th and U are more abundant in the Red Sea phosphorites than in the Nile Valley phosphorites. Furthermore, Th is not bio-available and it is mostly found in the residue as Th-bearing minerals. Uranium, unlike Th is bio-available and fractionates among all fractions, indicating that U accumulation is the result of various diagenetic processes.

Effects of different agricultural systems on organic matter and aggregation of a medium-textured soil in subtropical region

This work evaluates the impact of different agricultural systems on the humic fractions of organic matter (SOM) and soil aggregation in a medium-textured soil in a subtropical region of Brazil. Three managed areas and a reference area were evaluated: permanent pasture (PP), no-till (NT), no-till+Brachiaria (NT+B) and native forest (NF). Deformed soil samples were collected in the layers 0-0.05; 0.05-0.10; 0.10-0.20 and 0.20-0.40 m, and unformed soil samples in the layers 0-0.05 and 0.05-0.10 m. After collection, total organic carbon (TOC) analysis, chemical fractioning of SOM and aggregate stability analysis were performed. The PP area presented the highest TOC and C-FA contents in the first three layers evaluated. In the 0.10-0.20 m layer, the C-HUM contents in the NT+B area were 1.9 times higher than in the NT area, and in 0.20-0.40 m they were 6.6 times higher. The PP area obtained the best structural indicators, especially higher WMD, GMD and % of macroaggregates. The two areas using direct seeding presented a percentage of macroaggregates higher than 37.28% in the superficial layer. The PP management provided increases in TOC levels and, consequently, humic substances, besides the formation of more stable aggregates. The NT+B system showed promise in increasing TOC and humic substances, especially at depth, even with a short implementation period. The increase in TOC and humic substances provided by the grasses contributes to the formation of more stable aggregates and, consequently, to the improvement of the quality of medium-textured agricultural soils. Keywords: aggregate stability, carbon fractions, climate change, humic substances.

Geochemical characteristics and environmental implication of rare earth elements in sediments from the Three Gorges Reservoir, China

The construction and operation of the Three Gorges Dam occluded sediment transportation in the Yangtze River. However, the sources, transport processes, and environmental impacts of these sediments on the Three Gorges Reservoir (TGR) remain unclear. Here, we used rare earth elements (REEs) to trace the transport pathways of sediments in the TGR, China. Geochemical characteristics including the chemical composition and fractionation, temporal and spatial distribution, and potential sources of REEs were also evaluated in this study. The individual REEs concentration in the TGR sediments followed the Oddo-Harkins rule, with the mean REEs value of 207.33 μg/g. REEs concentrations in the midstream were higher than those in the upstream and downstream of the TGR. Statistical analysis showed that water impoundment phase had no significant influence on the distribution of REEs. TGR sediments are mainly derived from terrigenous detrital particulates, characterized by a distinctive enrichment in light REEs, with its percentage higher than 90 % of the total REEs. The significant positive correlation among the REEs confirmed that they are co-existed and shared the similar sources. Multiple provenance analysis approaches using discriminant function analyses, provenance indices, and La/Yb-La/Sm-Gd/Yb ternary diagrams further indicated that the REEs in sediments originated from the weathering of mudstone in the basin of TGR. After periodic water level fluctuation for more than six years, the chemical compositions of REEs in TGR sediments slightly differed from those of the Yangtze River sediments before TGR construction, but were similar to those of the downstream of the Yangtze River. Therefore, this study indicated that the construction and operation of the TGR changed the chemical compositions and the origin of the sediments in the Yangtze River, which can provide useful insights into the transport pathways of TGR sediments and their impacts on the fluvial environment.

Exploring the primary magnetic parameters affecting chemical fractions of heavy metal(loid)s in lake sediment through an interpretable workflow

The magnetic properties of lake sediments account for close relationships with heavy metal(loid)s (HMs), but little is known about their relationships with chemical fractions (CFs) of HMs. Establishing an effective workflow to predict HMs risk among various machine learning (ML) methods in conjunction with magnetic measurement remains challenging. This study evaluated the simulation efficiency of nine ML methods in predicting the risk assessment code (RAC) and ratio of the secondary and primary phases (RSP) of HMs with magnetic parameters in sediment cores of a shallow lake. The sediment cores were collected and sliced, and the total amount and CFs of HMs, as well as magnetic parameters, were determined. Support vector machine (SVM) outperformed other models, as evidenced by coefficient of determination (R2) > 0.8. Interpretable machine learning (IML) methods were employed to identify key indicators of RAC and RSP among the magnetic parameters. Values of χARM, HIRM, χARM/χ, and χARM/SIRM of sediments ranging in 220–500 × 10−8 m3/kg, 30–40 × 10−5Am2/kg, 15–25, and 0.5–1, respectively, indicated the potential ecological risks of Cd, Hg, and Sb. This study offers new perspectives on the risk assessment of HMs in lake sediments by combining magnetic measurement with IML workflow.

Biogenic calcium improved Cd2+ and Pb2+ immobilization in soil using the ureolytic bacteria Bacillus pasteurii

Bioremediation based on microbial-induced carbonate precipitation (MICP) was conducted in cadmium and lead contaminated soil to investigate the effects of MICP on Cd and Pb in soil. In this study, soil indigenous nitrogen was shown to induce MICP to stabilize heavy metals without inputting exogenous urea. The results showed that applying Bacillus pasteurii coupled with CaCl2 reduced Cd and Pb bioavailability, which could be clarified through the proportion of exchangeable Cd and Pb in soil decreasing by 23.65 % and 12.76 %, respectively. Moreover, B. pasteurii was combined separately with hydroxyapatite (HAP), eggshells (ES), and oyster shells (OS) to investigate their effects on soil heavy metals' chemical fractions, toxicity characteristic leaching procedure (TCLP)-extractable Cd and Pb as well as enzymatic activity. Results showed that applying B. pasteurii in soil significantly decreased the heavy metals in the exchangeable fraction and increased them in the carbonate phase fraction. When B. pasteurii was combined with ES and OS, the content of carbonate-bound Cd increased by 114.72 % and 118.81 %, respectively, significantly higher than when B. pasteurii was combined with HAP, wherein the fraction of carbonate-bound Cd increased by 86 %. The combination of B. pasteurii and biogenic calcium effectively reduced the leached contents of Cd and Pb in soil, and the TCLP-extractable Cd and Pb fractions decreased by 43.88 % and 30.66 %, respectively, in the BP + ES group and by 52.60 % and 41.77 %, respectively, in the BP + OS group. This proved that MICP reduced heavy metal bioavailability in the soil. Meanwhile, applying B. pasteurii and calcium materials significantly increased the soil urease enzyme activity. The microstructure and chemical composition of the soil samples were studied, and the results from scanning electron microscope, Fourier transform infra-red spectroscopy, and X-ray diffraction demonstrated the MICP process and identified the formation of CaCO3, Ca0.67Cd0.33CO3, and PbCO3 in heavy metal-contaminated soil.

β-glucans from Agaricus bisporus mushroom products drive Trained Immunity.

Macrofungi, such as edible mushrooms, have been used as a valuable medical resource for millennia as a result of their antibacterial and immuno-modulatory components. Mushrooms contain dietary fibers known as β-glucans, a class of polysaccharides previously linked to the induction of Trained Immunity. However, little is known about the ability of mushroom-derived β-glucans to induce Trained Immunity. Using various powdered forms of the white button mushroom (Agaricus bisporus), we found that mouse macrophages pre-treated with whole mushroom powder (WMP) displayed enhanced responses to restimulation with TLR ligands, being particularly sensitive to Toll-like receptor (TLR)-2 stimulation using synthetic lipopeptides. This trained response was modest compared to training observed with yeast-derived β-glucans and correlated with the amount of available β-glucans in the WMP. Enriching for β-glucans content using either a simulated in-vitro digestion or chemical fractionation retained and boosted the trained response with WMP, respectively. Importantly, both WMP and digested-WMP preparations retained β-glucans as identified by nuclear magnetic resonance analysis and both displayed the capacity to train human monocytes and enhanced responses to restimulation. To determine if dietary incorporation of mushroom products can lead to Trained Immunity in myeloid cells in vivo, mice were given a regimen of WMP by oral gavage prior to sacrifice. Flow cytometric analysis of bone-marrow progenitors indicated alterations in hematopoietic stem and progenitor cells population dynamics, with shift toward myeloid-committed multi-potent progenitor cells. Mature bone marrow-derived macrophages derived from these mice displayed enhanced responses to restimulation, again particularly sensitive to TLR2. Taken together, these data demonstrate that β-glucans from common macrofungi can train innate immune cells and could point to novel ways of delivering bio-available β-glucans for education of the innate immune system.

Fish Physiologically Based Toxicokinetic Modeling Approach for In Vitro-In Vivo and Cross-Species Extrapolation of Endocrine-Disrupting Chemicals in Risk Assessment.

High-throughput in vitro assays combined with in vitro-in vivo extrapolation (IVIVE) leverage in vitro responses to predict the corresponding in vivo exposures and thresholds of concern. The integrated approach is also expected to offer the potential for efficient tools to provide estimates of chemical toxicity to various wildlife species instead of animal testing. However, developing fish physiologically based toxicokinetic (PBTK) models for IVIVE in ecological applications is challenging, especially for plausible estimation of an internal effective dose, such as fish equivalent concentration (FEC). Here, a fish PBTK model linked with the IVIVE approach was established, with parameter optimization of chemical unbound fraction, pH-dependent ionization and hepatic clearance, and integration of temperature effect and growth dilution. The fish PBTK-IVIVE approach provides not only a more precise estimation of tissue-specific concentrations but also a reasonable approximation of FEC targeting the estrogenic potency of endocrine-disrupting chemicals. Both predictions were compared with in vivo data and were accurate for most indissociable/dissociable chemicals. Furthermore, the model can help determine cross-species variability and sensitivity among the five fish species. Using the available IVIVE-derived FEC with target pathways is helpful to develop predicted no-effect concentration for chemicals with similar mode of action and support screening-level ecological risk assessment.

The effect of heavy metals mobility on their bioavailability in Güllük Lagoon, Aegean Sea

The mobility and bioavailability of heavy metals (HMs) were investigated in the Güllük Lagoon, the southern part of the Aegean Sea. Total concentrations and chemical fraction concentrations of Cd, Pb, Cu, Fe, Mn, Zn and Hg in surface sediment, total concentrations of these metals in Mugil cephalus tissues (liver, gill, skin and muscle) and aquatic plant Ludwigia stolonifera were determined using atomic absorption spectrometry (AAS). The Risk Assessment Code used to evaluate the mobility and bioavailability of metals was found to be the highest for Cd, and the Geoaccumulation Index, which indicates the pollution level in the sediment, was found to be the highest for Hg. It was determined that Hg concentrations in the muscle tissue of M. cephalus were higher than the threshold values. Furthermore, the values of the chemical fraction stages and risk assessment code indicated that Cd and Hg were mobile in surface sediment and biota. Based on the results of the study, it can be argued that the anthropogenic activities in the region affect the concentrations of especially Cd, Cu, and Hg in sediment and biota. The high metal concentrations measured in the study show that the study area is under the effect of thermal power plants, domestic, industrial, and agricultural wastes brought by the Sarıçay River, and aquaculture, which is intense in the region. As a result, it is emphasized that potential sources of Hg, Cd, and Cu pollution should be determined and precautions should be taken to protect the ecosystem and public health in Güllük Lagoon in this study.

Chemical fractionation and mobility factor of some heavy metals in refuse dumpsite soil in Awka Metropolis, Anambra State, Nigeria

The geochemical forms of some heavy metals in refuse dump soils at Agu-Awka, Awka metropolis was studied in order to assess the mobility and bioavailability of the metals and hence their potential environmental risk. Exchangeable fraction (F1) contained the % fraction of 13.23% for Cd, 17.43% for Cr, 14.63% for Pb, 12.40% for Ni, 25.34% for Zn and 15.92% for Mn and these are in the order of Zn ˃ Cr ˃ Mn ˃ Pb ˃ Cd ˃ Ni. The carbonate fraction (F2) contained the % fraction of 17.08% for Cd, 17.84% for Cr, 9.20% for Pb, 28.32% for Ni, 13.76% for Zn and 8.49% for Mn and these are in the order of Ni ˃ Cr ˃ Cd ˃ Zn ˃ Pb ˃ Mn. Lead was predominantly associated with organic fraction with a result of 42.64% followed by chromium and manganese with the values of 22.48% and 20.00% respectively. The organic bound metals were in the abundance trend of Pb ˃ Cr ˃ Mn ˃ Cd ˃ Ni ˃ Zn. The highest values of metal in Fe-Mn oxide phase was manganese with a value of 32.18%, followed by cadmium with the value of 21.76%. The values of the other metals bound to this phase were 17.52%, 16.64%, 13.99% and 12.90% for Zn, Ni, Cr, and Pb respectively. Zinc with the value of 32.20% was predominantly associated with the residual fraction. The other metals bound to this phase had their values to be 30.13% for cadmium, 28.24% for chromium, 20.61% for lead, 29.41% for nickel and 23.37% for manganese. The mobility factor values of the metals were relatively low and they followed the order of Ni > Zn > Cr > Cd > Mn > Pb. That notwithstanding, soils from studied area should be carefully monitored to prevent the release of these metals due to redox reactions which may make them available to plants through absorption.

Changes in Milk Protein Functionality at Low Temperatures and Rennet Concentrations

This study aimed to evaluate the influence of low-concentration rennet on the chemical, rheological characteristics, and protein fractions of skim milk (SM) at 4 ± 1 °C. Skimmed milk (SM) was divided into four lots of 500 mL, and diluted rennet (1:10,000) was added at different levels at 4 ± 1 °C. The treatments included control (no rennet), T1 (0.001 mL/rennet), T2 (0.01 mL rennet), and T3 (0.1 mL rennet) treatments, which were incubated for 24 h. The sampling was performed at 0, 1, 2, 6, 12, and 24 h, and the SM after incubation time was heated to 73 °C/16 s to denature the rennet enzyme. Skim milk samples (SMS) (control and rennet-added samples) were evaluated for proximate composition, capillary gel electrophoresis (CGE), hydrodynamic diameter, zeta potential, and rheology at 0, 1, 2, 6, 12, and 24 h. Foaming ability, foaming stability, water-holding capacity (WHC), oil emulsifying activity (OEA), and emulsion stability (ES) were performed at 0, 12, and 24 h of incubation time. There was a significant (p < 0.05) increase in non-proteins by 0.50% and in non-casein nitrogen by 0.81% as incubation progressed. The results showed that aggregation or curd was not formed during storage time. The CGE data indicated that increasing the rennet concentration had a significant (p < 0.05) effect on decreasing κ-CN, and breakdown increased at higher levels of rennet usage. There was a significant (p < 0.05) increase in the hydrodynamic diameter and a decrease in the zeta potential values in rennet-added samples at the end of the incubation time (24 h). The rheological results showed no changes in the storage modulus (G′), loss modulus (G″), or viscosity values. Increasing the rennet amount and storage time led to a significant (p < 0.05) decrease in the foaming ability and foaming stability and a significant (p < 0.05) increase in the oil emulsifying activity and emulsion stability of rennet-added SMS. This study concluded that milk protein functionality can be changed without aggregating or curd formation, and rennet milk can be processed.

Chemical fractionation of elements in leaf-deposited particulate matter of an urban area in India

Chemical fractionation of elements in leaf-deposited particulate matter of an urban area in India

Zinc speciation in highly weathered tropical soils affected by large scale vegetable production

Agriculture in highly weathered tropical soils often requires considerable application of lime and fertilizers to ensure satisfactory plant nutrient levels. The consequences of these continue long-term applications is not well understood may induce changes in soil chemical properties, the abundance, and speciation of potentially toxic trace element and as well as of micronutrients in agriculture soils. In this study, we evaluated the adsorption (at pH 5) and speciation of Zn in tropical soils (both agricultural and native vegetation) as a function of fertilization and contact time using chemical fractionation analyses and X-ray absorption spectroscopy. The soils overall had high Zn adsorption capacities (∼ 700 mg kg-1), but the agricultural soil was approximately 30 % higher than of the soil under native vegetation, and the proportion of Zn in the mobile fraction was 35 % in native vegetation and 21 % in agricultural soils. Zn speciation via linear combination analysis showed a strong relationship with soil mineralogical composition and reveled that Zn associated with organic matter decreased while Zn associated with P increased after the conversion of soils from native vegetation to highly fertilized soil. Aluminosilicate soil minerals were identified as major sinks of soil Zn, accounting for 34 % of total Zn retention regardless of soil origin and land use. Association of Zn with phosphate (i.e., hopeite) was observed in the agricultural soil samples, which might be an unexpected Zn-bearing mineral in highly weathered tropical soils and could have impacts on Zn plant nutrition.

More than colorful: phosphorus allocation to major chemical fractions shifts during leaf development in species exhibiting delayed greening

The colorful “delayed leaf greening” is a common but overlooked phenomenon in phosphorus (P)-limited environments in habitats in tropical, subtropical and temperate forests, but the physiological mechanism underpinning it remains unclear. It is important to understand how allocation of phosphorus to major leaf P fractions shifts during leaf development, as a strategy for utilizing P efficiently. We measured concentrations of leaf nitrogen and P and five chemical P fractions, and eight leaf chemical element concentrations (K, Ca, Mg, Mn, Fe, Cu, Zn and Se) in young and mature leaves of six woody plants exhibiting delayed greening in China. We also measured leaf mass per area, photosynthetic rate, photosynthetic phosphorus-use efficiency, and soil nutrient concentrations. The results indicate six species exhibiting delayed greening had different leaf P concentrations during leaf development, but the same nitrogen concentrations. We further show major leaf chemical P fractions like metabolite P, nucleic acid P and lipid P showed differences in young and mature leaves. The concentration of lipid P, nucleic acid P, Pi and residual P significantly decreased from young to mature leaves, while that of metabolite P was constant. There was a greater allocation of P to phospholipids and metabolite P in mature leaves. The concentration of Cu and K were significantly higher in young leaves. This study provides new insight to investigate the roles of different P fractions in young and mature leaves, and how the allocation shifts for plants to utilize phosphorus.

Spatial variation of soil organic matter and metal mobility in wetland soils: Implications for biogeochemical processes in lateritic landscape

The evolution of the lateritic landscape over time changes the path of pedogenesis and soil hydrology. The occurrence of upland wetlands in the savannah flat plateau transforms well-drained lateritic soils into hydric soils enriched in organic matter. We investigated the composition of soil organic matter (SOM) produced in a wetland and their link with the mineral constituents of soil and their contribution to the mobility of Si, Fe, and Al in the soil. Six tranches were opened in a soil catena located from the plateau toward the center of the wetland, representing different hydromorphic features. Soil morphology was described, and chemical, physical and mineralogical analyses were performed to evaluate soil properties. Chemical fractionation of Soil Organic Matter (SOM) was performed and total organic carbon (TOC), dissolved organic carbon (DOC), particulate organic carbon (POC), and water-extractable organic matter (WEOM) were determined in the soil horizons. Metal complexing properties of DOM were determined using an excitation-emission matrix of fluorescence. The occurrence of Fe eluviation in the superficial horizons, Fe2O3 enrichment in the mottled horizons, and ferricrete formation in the center of the wetland were observed. Geochemical transfer assessment and the variation of oxides within the horizons showed that Fe2O3 and SiO2 were more mobile than Al2O3, whose variability in the gley horizon reflected the mobility of Fe2O3 and SiO2. The stability constants of Al and Cu showed an increase with the depth for WEOM and SOM. The pattern of the organic carbon fraction varied according to the level of hydromorphy and soil depth. It was also observed an increase in the C/N ratio with depth, possibly related to the reduced bioavailability of DOC due to its adsorption with soil solids.

Assessment of metal pollution and effects of physicochemical factors on soil microbial communities around a landfill

The physicochemical properties, chemical fractions of six metals (Cu, Zn, Pb, Cd, Cr, and Mn), and microbial communities of soil around a typical sanitary landfill were analyzed. The results indicate that soils around the landfill were from neutral to weak alkalinity. The contents of organic matter (OM), total nitrogen (TN), total phosphorous (TP), and activities of catalase, cellulase, and urease were significantly higher in landfill soils than those in background soils. Negative correlations were found between pH and metals. Cr was the dominant metal. Cu, Pb, Cr, and Mn were accumulated in the nearby farmland soils. Cd had the highest percentage of exchangeable fraction (33.7%−51.8%) in landfill and farmland soils, suggesting a high bioavailability to the soil environment affected by the landfill. Pb, Cr, and Mn existed mostly in oxidable fraction, and Cu and Zn were dominant in residual fraction. There was a low risk of soil metals around the landfill based on the RI values, while according to RAC classification, Cd had high to very high environmental risk. The MisSeq sequencing results showed that Actinobacteria, Proteobacteria, Chloroflexi, and Acidobacteria were the dominant phyla of bacteria, and the most abundant phylum of fungi was Ascomycota. The NMDS analysis revealed that the landfill could influence soil fungal communities more intensely than bacterial communities. TN, cellulase, and bioavailable metals (Pb-Bio and Cr-Bio) were identified to have main influences on microbial communities. Pb-Bio was the most dominant driving factor for bacterial community structures. For fungi, Pb-Bio was significantly negatively related to Olpidiomycota and Cr-Bio had a significantly negative correlation with Ascomycota. It manifests that bioavailable metals play important roles in assessing environmental risks and microbial community structures of soil around landfill.

Changes in chemical fractionation of copper and zinc in soil as a function of incubation moisture content and organic matter amendments

Copper and zinc are essential micronutrients that are potentially toxic when present in excess in soils. Their bioavailability depends on their speciation in soil, but this may vary with environmental conditions. Aeration and hence redox conditions, and organic matter amendments are among the factors likely to cause variation on metal fractionation. We have monitored the chemical fractionation of both native and added copper and zinc in a clay loam top soil during a 5-month laboratory incubation. The effects of aeration (moist soil or flooded) and addition of two organic matter amendments, alfalfa straw or leaf compost, were studied. Metal spike was more labile than legacy metal, and was slowly redistributed over the incubation period. Organic matter caused short-lived flushes of metals, attributed to metal chelation with soluble organic matter. This effect was greater for straw than for more stable compost. There was no evidence that added organic matter increased the capacity of soil organic matter to immobilise metal. Flooding solubilized soil metal (hydr)oxides, releasing legacy Cu and Zn, but with less effect on the capacity to immobilise metal spike. Effects of flooding and organic matter addition were not additive. Both metals appear to be precipitated as sulphides under reducing conditions, and accounted for in the acid soluble phase. Monitoring the dynamics of metal distribution gives a more comprehensive understanding of underlying processes than would a single measurement, and is closer to in campo conditions than slurry microcosms.

Influence of land use on spatial distribution of mobile phosphorus forms in the sediment of a tropical semi-arid reservoir

Changes in land use and land cover influence the transport of nutrients, mainly phosphorus (P), to aquatic ecosystems. P can be available in the water column to primary producers' assimilation or be stored in different forms in limnic sediment. Therefore, this study aims to analyze the impact of land use and land cover on the spatial distribution of phosphorus forms in the sediment of a tropical semi-arid reservoir. We hypothesize that agriculture, exposed soil and the presence of floodable vegetation increase the amount of mobile phosphorus in the sediment and the sediment closer to the dam show a greater amount of mobile phosphorus due to the confluence of the flows. The classification of land use and land cover was carried out through supervised analysis at the level of the reservoir's drainage basin and area of influence. Sediment samples from the reservoir were collected at four different sampling points within the influence of two sub-basins. P forms were obtained through chemical fractionation of these sediment samples along the reservoir. Sparse Caatinga was the predominant land cover in the drainage basin and in the influence area, accounting for >50 % of these areas. This land cover represents a risk for nutrient transport to aquatic environments. The sediment samples from Boqueirão reservoir exhibited a high amount of phosphorus, mainly in the mobile forms. These forms were heterogeneously distributed throughout the reservoir. Agriculture activities, exposed soil, and floodable vegetation, influence the distribution and increase of mobile forms of phosphorus in the reservoir sediment. This suggests the need for specific strategies for manage these activities properly. Additionally, the sediment closest to the dam showed a lower amount of mobile phosphorus compared to samples further upstream.

Insight into heavy metal chemical fractions in ash collected from municipal and industrial waste incinerators in northern Vietnam.

This investigation involved the collection of fly ash and bottom ash specimens from seven waste incinerators situated in the northern provinces of Vietnam, aimed at assessing the composition and distribution patterns of five chemical fractions of heavy metals (Pb, Cr, As, Cd Cu, and Zn) present in incinerator waste ash. The outcomes reveal that fly ash exhibited a relatively elevated concentration of industrial waste metals (25-66%) such as As, Cd, and Pb primarily in exchangeable (F1) and carbonate fractions (F2), which are mobile forms susceptible to environmental dissolution and consequential bioaccumulation posing health risks to humans. The predominant states of the metals Cr, Cu, and Zn were identified as residual, Fe-Mn oxide, and carbonate, respectively, with their relative proportions showing minimal variation. Conversely, heavy metals were predominantly present in residual residue and Fe-Mn bound form (F3) in bottom ash derived from both residential and commercial waste incineration operations. The non-carcinogenic hazard indices (HI) associated with the examined metals, ranked for both adults and children, were as follows: Pb > Cr > As > Cd > Cu > Zn. Notably, the HI values for Pb, Cr, and As exceeded the permissible threshold (HI > 1) for children. However, the risk of As, Cd, and Pb-related cancer via exposure pathways remained within acceptable limits for both age groups. Conversely, the probability of carcinogenic effects attributable to Cr surpassed the permissible threshold (>10-4), indicating significant health concerns associated with heavy metals in waste incinerators for humans, particularly children.

Monitoring the Centennial Variation of Heavy Metals in Lake Sediments and Influencing Factors Using Environmental Magnetism and Machine Learning Methods

The association between the magnetic properties of lake sediments and heavy metal(loid)s (HMs) is well-documented; however, their correlation with the chemical fractions of HMs remains under-investigated. Developing a robust workflow for predicting HMs risk utilizing various machine learning techniques in conjunction with magnetic analysis presents a complex challenge. This study assessed the predictive efficacy of nine machine learning models for determining the chemical fractions of HMs, employing magnetic parameters derived from sediment cores in a large, shallow lake. These models encompassed random forest, support vector machine, relevance vector machine, extreme gradient boosting, principal component regression, multivariate adaptive regression splines, gradient boosting with component-wise linear models, and lasso and elastic-net regularized generalized linear models. The support vector machine model demonstrated superior performance, achieving coefficient of determination values surpassing 0.8 in both training and testing phases. Through interpretable machine learning approaches, key drivers of HMs were identified among magnetic and physicochemical indicators. Magnetic susceptibility values, high coercivity remanent magnetization, ratios of anhysteretic remanent magnetization to magnetic susceptibility, and anhysteretic remanent magnetization to saturation isothermal remanent magnetization within specific ranges exhibited a positive correlation with Cd, Hg, and Sb. This research significantly advances our understanding of HMs risk assessment in lake sediments by leveraging accessible magnetic measurements within an interpretable machine learning framework.