Pore Water Concentrations Research Articles

Integrated assessment of heavy metal pollution in the great bačka canal: Comparing active and passive sampling methods.

This study investigates the environmental risks posed by heavy metals in sediment from the Great Bačka Canal using both active and passive sampling methods. The necessity of this research lies in the critical need to address sediment contamination in ecological hotspots and enhance sediment management practices. Active sampling revealed total heavy metal concentrations, while sequential extraction showed bioavailability varied across metal fractions. Passive sampling with SPeeper™ quantified freely dissolved metal concentrations in sediment pore water, identifying zinc (41μg/L) as the most bioavailable metal. Risk indices, including Igeo (geo-accumulation index) and IWCTU (interstitial water criteria toxic units), revealed low to moderate contamination levels. Although copper content classified the sediment as extremely polluted (195.7mg/kg), its low bioavailability (16μg/L in pore water) mitigates immediate ecological risks. These findings emphasize the importance of integrating passive sampling in regulatory frameworks for a realistic environmental risk assessment of sediments.

Dolomite dissolution, pH neutralization, and potentially toxic element immobilization in stormwater bioretention beds.

The importance of pH in stormwater bioretention beds cannot be overstated since it impacts plant and microbial populations and removal of potentially toxic elements (PTEs) from stormwater runoff. This study investigated the effects of dolomite amendment on pH neutralization and subsequent PTE immobilization in bioretention media. To assess dolomite dissolution, pH neutralization, and PTE immobilization, engineered bioretention media was amended with different dolomite ratios and samples of dolomite-amended media were collected from two bioretention beds, one and two months after installation. The effects of inflow conditions and operational time on dolomite dissolution and PTE immobilization were investigated through a column study. Laboratory batch experiments revealed that pH neutralization was fast and reached the recommended pH range of 5 to 8 within 5min. Among the 1-D column conditions, intermittent inflow had the highest porewater Mg and Ca concentrations, indicating greater dolomite dissolution. Batch experiments on field-collected media showed that pH neutralization was substantial within 1month, and continued during the second month, due to dolomite dissolution. Dissolved (batch experiments) and column porewater Mg and Ca concentrations supported instantaneous Ca and a relatively slow Mg dissociation during dolomite dissolution. Among the monitored PTEs, dissolved and porewater concentrations (μg/L) were found to decrease with time, in the order Mn>Fe>Zn>Cu>Pb>Cd, with Cr mainly undetected in all experimental conditions. However, as pH became neutralized to slightly basic (pH~8), dissolved and porewater As concentrations increased. The study suggests that pH neutralization and PTE immobilization depend on the soil-to-dolomite ratio and hydrological properties such as inflow rate, dry-wet cycle, and soil-water contact time. Dolomite amendment to engineered media can be an effective measure for intercepting contaminants, improving ecosystem health, and enhancing biochemical contaminant breakdown, though consideration should be given to bioretention bed design features and system hydrology.

Foraminiferal denitrification and deep bioirrigation influence benthic biogeochemical cycling in a seasonally hypoxic fjord

Benthic macro- and micro-biota often play significant roles in controlling the biogeochemical dynamics in sediments. Their activity can be influenced by oxygen availability and impacted by the rise in global hypoxia in coastal regions over the last decades. To understand how these organisms interact with coastal hypoxia and influence sediment biogeochemistry, we undertook a study of early diagenesis in Bedford Basin, a seasonally hypoxic fjord on the West Atlantic coast in Nova Scotia, Canada, using a combination of observations and reaction-transport modeling. We observed that the seafloor was a source of ammonium and sink of nitrate with average fluxes of 2.2 ± 1.8 and −0.9 ± 0.7 mmol m−2 d−1 respectively. The diffusive oxygen uptake was 14 ± 4.6 mmol m−2 d−1 and the total organic carbon content in collected sediment cores was 5–7 % with a C/N ratio of ∼10. The pyrite content increased steadily from 0.5 wt% Fe at surface to ∼2 wt% Fe at 20 cm depth. Hydrogen sulfide was negligible down to 25 cm depth most of the time. The sediment was inhabited by tube-forming polychaete Spiochaetopterus sp. that formed tubes up to ∼30 cm in length. The living foraminiferal assemblage in the top 5 cm sediment was found to be dominated (>85 %) by nitrate-storing and denitrifying benthic foraminifera Stainforthia fusiformis. These observations were used to develop and constrain a biogeochemical reaction-transport model. The model results suggest that the observed decrease in porewater concentrations of ammonium and dissolved inorganic carbon below 5 cm depth, was due to deep bioirrigation by tubeworms, accounting for almost 50 % of the benthic efflux. The model further revealed that the deep bioirrigation along with bioturbation and iron cycling prevented accumulation of free sulfide in the top 25 cm sediment despite oxygen penetration depths of ∼1 mm. Modelled organic carbon and nitrogen deposition was 25.2 and 2.9 mmol m−2 d−1 with burial efficiencies of 23 % and 17 %, respectively. The model indicated a total denitrification rate of 1.3 mmol N m−2 d−1 that was largely (∼70 %) driven by benthic foraminifera. This study reports the first evidence of foraminiferal denitrification in western Atlantic coastal sediments, and suggests that eukaryote mediated denitrification is an important driver of sediment N-loss in seasonally hypoxic environments, a process that has been traditionally assumed to be carried out by prokaryotic microbes.

Integrating ex situ biomimetic extraction analyses into contaminated sediment assessment and management decisions.

This study evaluated a novel ex situ passive sampling biomimetic extraction (BE) method to estimate toxic potency in sediments. Gas chromatography with flame ionization detection (GC-FID) analysis of polydimethylsiloxane fibers equilibrated with field sediments was used to quantify bioavailable polyaromatic hydrocarbons (PAHs) and other unresolved, site-specific contaminant mixtures. This method is biomimetic because contaminants partition to the fiber based on hydrophobicity and abundance, and GC-FID quantification accounts for all constituents absorbed to the fiber that may contribute to toxicity. This measurement was compared with conventional approaches that rely on bulk sediment or porewater measurements of a targeted suite of PAHs. The specific objectives of the study were to (1) describe the BE method and explain measurement translation into toxic units (TUs); (2) report sediment BE data collected across 17 diverse field sites; (3) compare TUs predicted from (i) equilibrium partitioning (EqP) calculations based on sediment total organic carbon and bulk PAH chemistry, (ii) PAH porewater concentrations derived using ex situ passive sampling, and (iii) BE concentrations; and (4) discuss implications of this analysis for benthic toxicity assessment. Results showed that TUs obtained from EqP calculations were typically 10× higher than TUs derived from measured porewater PAH concentrations, indicating reduced PAH bioavailability in field sediments. Toxic units derived using the new BE method were more conservative than EqP in one-third of the sediments investigated, which was attributed to unquantified sediment contaminants, possible fiber fouling in the more contaminated sediments, and potential background interferences in less contaminated sediments. Preliminary data are also presented, showing that fluorometric analysis provides a simpler, promising alternative for estimating sediment BE concentrations. Based on this analysis, a decision-support framework is proposed using EqP and BE based TU metrics. Future research priorities are described for supporting framework implementation and extending use of BE analyses to remedial design and monitoring.

Sediment Ballet: Unveiling the Dynamics of Metal Bioavailability in Sediments Following Resuspension and Reequilibration.

Assessing the risk of metal-contaminated sediments under disturbed conditions is challenging due to the lack of methods that capture instant changes in metal bioavailability. Existing approaches provide inadequate understandings of the processes regulating metal bioavailability under nonequilibrium conditions. Experiments were conducted to improve our understanding of the metal bioavailability dynamics induced by sediment resuspension and subsequent redeposition (reequilibration). An isotopically modified bioassay, a novel stable isotope tracing technique, was used to measure metal bioavailability (assimilation rates) to clams within short time windows. Changes in metal partitioning were characterized by porewater analysis using in situ extraction and the diffusive gradients in thin-films technique. Results showed that sediment resuspension released metals into porewater, while reequilibration scavenged metals from the porewater. The assimilation rates of Ni, Cu, and Pb increased with the resuspension time, aligning with increasing porewater concentrations. Unexpectedly, during reequilibration, the metal assimilation rates did not decrease. The discrepancies between bioavailability to the clam and porewater extrapolations may be due to differing sustained conditions of metals in sediments. Overall, this study unveils the metal bioavailability dynamics in nonequilibrium sediments, which could not be accurately predicted relying solely on porewater analysis. Incorporating rapid bioassays to determine bioavailability offers a valuable tool for robust ecological risk assessment.

Control of arsenic methylation in paddy soils by iron nanoparticles

Rice, as the most essential food grain, is frequently exposed to high concentrations of arsenic. Among the arsenic species, dimethylarsenate (DMAs(V)) is preferentially translocated from paddy soils to rice grains, posing serious threats to food safety and yield. Herein, we report an efficient strategy for DMAs(V) mitigation in paddy soils with nanoscale Zero-Valent Iron (nZVI). Species and concentrations of arsenic in paddy porewater were monitored during a 28-d soil-water incubation. Effects of nZVI dose towards microbial sulfate reduction and methane generation potential in paddy soils, which are crucial for arsenic methylation and demethylation, were analyzed via metagenomic sequencing. Results demonstrated that the maximal DMAs(V) concentration in paddy porewater decreased from 0.37 to 0.04 μM in arsenic-contaminated paddy soils with nZVI dose increasing from 0 to 5.0 g/kg. Accordingly, the maximal concentration of inorganic arsenite (iAs(III)), which is the precursor of DMAs(V), decreased from 1.39 to 0.23 μM. Furthermore, the application of nZVI reshaped the structure of microbial community in paddy soils. Specifically, the relative abundance of δ-proteobacteria involved in sulfate reduction, which is crucial for iAs(III) methylation, waned from 7.62 % to 3.17 %, while that of Methanomicrobia for DMAs(V) demethylation and methanogenesis proliferated from 7.03 % to 13.62 %, with nZVI dose increasing from 0 to 5.0 g/kg. Via simultaneous inhibition of DMAs(V) formation and acceleration of DMAs(V) transformation, nZVI efficiently controls the accumulation of DMAs(V) in paddy porewater. In conclusion, these findings prove the efficient performance for DMAs(V) mitigation with nZVI and uncover its underlying mechanisms.

Optimizing multi-surface modelling of available cadmium as measured in soil pore water and salt extracts of soils amended with compost and lime: The role of organic matter and reactive metal

The effectiveness of strategies to reduce cadmium (Cd) availability for crop uptake can be assessed using various measures of Cd availability, such as Cd concentration in pore water and Cd extracted with salt solutions. This study evaluated the performance of multi-surface modelling (MSM) to predict dissolved Cd in two Irish tillage soils treated with lime, zinc (Zn) and spent mushroom compost (SMC). Predictions were assessed against Cd measured in three solution media, i.e., 1 mM Ca(NO3)2 and 0.1 M CaCl2 extractions, as well as in soil pore water. Results indicate that reactive soil organic matter (SOM) may be underestimated using a single 0.1 M NaOH extraction in the investigated soils, leading to substantial overestimation of dissolved Cd by MSM, particularly at higher pH. Repeating the 0.1 M NaOH extraction three times substantially improved model predictions. Additionally, using reactive Cd determined by isotopic dilution instead of 0.43 M HNO3 improved model predictions for one of the soils that was rich in manganese (Mn) oxides, revealing a possible role of Mn oxides in determining the reactive Cd fraction. After optimizing reactive SOM and reactive Cd, residuals between predicted and measured Cd showed an increasing trend along with increasing solution pH and decreasing dissolved Cd. This is likely related to Cd binding to high affinity sites due to uncertainties in the binding parameters for these sites and/or to slow desorption kinetics for Cd bound to these sites. Despite significant variations in solution properties, including higher dissolved Ca and reactive dissolved organic matter (DOM), 1 mM Ca(NO3)2 extracts exhibited similar extractable Cd levels, model performance, and Cd speciation compared to soil pore water especially at higher pH. Thus, 1 mM Ca(NO3)2 can be a reliable proxy for soil pore water in assessing Cd availability for crop uptake in soils with circumneutral to alkaline pH.

Controlled soil monolith experiment for studying the effects of waterlogging on redox processes

Climate change induced mild and rainy winters may expose soils to more frequent and prolonged waterlogging in boreal regions. Resulting oxygen depletion induces reductive dissolution of iron (Fe) oxides further altering the stability of Fe-associated organic matter. Thus far, the impact of waterlogging on the coupled cycling of Fe and carbon (C) in upland arable soils remains unknown. We constructed a monolithic experimental system with 32 soil profiles (l = 63 cm, d = 15.2 cm) collected from two agricultural fields (silty clay, sandy loam) to study the effects of off-season waterlogging, overwintering cover crop and soil type on soil redox potential (Eh), Fe solubility, and movement of C and nitrogen (N) within the soil–plant-atmosphere continuum. Soil moisture, temperature, electrical conductivity, and Eh were continuously monitored, and soil pore water samples were collected at three soil depths. Here, we assess the systems suitability for studying coupled Fe and C dynamics in boreal climate, and investigate the treatment impacts on soil Eh, pH, reductive Fe dissolution and N concentration in pore water. Waterlogging led to reducing conditions in both soils down to 30 cm depth at the soil temperature (+4 to 12 °C) matching those of spring and autumn in southern Finland. The declining Eh and the slightly rising Fe concentration in porewater (max ∼ 10 µmol l−1) suggest that reductive dissolution of Fe could proceed even during mild winters if the duration of waterlogging exceeds 1–2 weeks. The study demonstrated that cover crops may accelerate the drop in soil Eh by removing bioavailable N, and hence controlling the availability of alternative electron acceptors (nitrate) in the soil. Thus, the simultaneous effects of cover crops on C inputs, and on N and water dynamics, all influencing redox reactions, emphasize the importance of incorporating vegetation into studies exploring the impacts of waterlogging on coupled dynamics of Fe and C.

Conventional and biodegradable microplastics affected arsenic mobility and methylation in paddy soils through distinct chemical-microbial pathways

The presence of microplastics (MPs) in paddy soil has become a growing concern, yet the influence of MPs on arsenic (As) dynamics in paddy soil remains largely unexplored. A 98-day microcosm experiment was conducted to investigate the impact of MPs on As behavior in As-contaminated paddy soil. The results revealed that conventional microplastics (CMPs) reduced As concentration in porewater by 25–38 %, but substantially increased the percentage of methylated As (% MeAs) in soil by 8–23 times under 5 % dosages after 98-day incubation. In contrast, at the end of incubation, biodegradable microplastics (BMPs) at 5 % dosages notably increased As concentration in porewater and % MeAs in soil by 2–9 times and 11–395 times, respectively. The combination of network analysis and Random-Forest analysis implied that CMPs might inhibit As mobility through enhancing microbial As(III) oxidation and promote As methylation by enriching arsM-carrying microbes. However, BMPs promoted As release mainly accompanying with microbial iron reduction, and enhanced As methylation through enriching fermenting bacteria (i.e., Clostridiaceae) and arsM-carrying organic matter degrading bacteria (i.e., Gemmatimonas and Nocardia). These findings might provide broaden insights into As cycling induced by MPs and contribute to the prevention of combined pollution from As and MPs in paddy soil.

Riparian Methylmercury Production Increases Riverine Mercury Flux and Food Web Concentrations.

The production and uptake of toxic methylmercury (MeHg) impacts aquatic ecosystems globally. Rivers can be dynamic and difficult systems to study for MeHg production and bioaccumulation, hence identifying sources of MeHg to these systems is both challenging and important for resource management within rivers and main-stem reservoirs. Riparian zones, which are known biogeochemical hotspots for MeHg production, are understudied as potential sources of MeHg to rivers. Here, we present a comprehensive quantification of the hydrologic and biogeochemical processes governing MeHg concentrations, loads, and bioaccumulation at 16 locations along 164 km of the agriculturally intensive Snake River (Idaho, Oregon USA) during summer baseflow conditions, with emphasis on riparian production of MeHg. Approximately one-third of the MeHg load of the Snake River could not be attributed to inflowing waters (upgradient, tributaries, or irrigation drains). Across the study reach, increases in MeHg loads in surface waters were significantly correlated with MeHg concentrations in riparian porewaters, suggesting riparian zones were likely an important source of MeHg to the Snake River. Across all locations, MeHg concentrations in surface waters positively correlated with MeHg concentrations in benthic snails and clams, supporting that riparian produced MeHg was assimilated into local aquatic food webs. This study contributes new insights into riparian MeHg production within rivers which can inform mitigation efforts to reduce MeHg bioaccumulation in fish.

A Novel Landfill Liner Material for Solidified Lake Sediment Based on Industrial By-Product and Construction Waste: Engineering Behavior and Cr(VI) Breakdown Characteristics

Engineering sludge, industrial waste, and construction waste are marked by high production volumes, substantial accumulation, and significant pollution. The resource utilization of these solid wastes is low, and the co-disposal of multiple solid wastes remains unfeasible. This study aimed to develop an effective impermeable liner material for landfills, utilizing industrial slag (e.g., granulated blast furnace slag, desulfurized gypsum, fly ash) and construction waste to consolidate lake sediment. To assess the engineering performance of the liner material based on solidified lake sediment presented in landfill leachate, macro-engineering characteristic parameters (unconfined compressive strength, hydraulic conductivity) were measured using unconfined compression and flexible wall penetration tests. Simultaneously, the mineral composition, functional groups, and microscopic morphology of the solidified lake sediment were analyzed using microscopic techniques (X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy + energy dispersive spectroscopy). The corrosion mechanism of landfill leachate on the solidified sediment liner material was investigated. Additionally, the breakdown behavior of heavy metal Cr(VI) within the solidified sediment liner barrier was investigated via soil column model experiments. The dispersion coefficient was computed based on the migration data of Cr(VI). Simultaneously, the detection of Cr(VI) concentration in pore water indicated that the solidified sediment liner could effectively impede the breakdown process of Cr(VI). The dispersion coefficient of Cr(VI) in solidified sediments is 5.5 × 10−6 cm2/s–9.5 × 10−6 cm2/s, which is comparable to the dispersion coefficient of heavy metal ions in compacted clay. The unconfined compressive strength and hydraulic conductivity of the solidified sediment ranged from 4.90 to 5.93 MPa and 9.41 × 10−8 to 4.13 × 10−7 cm/s, respectively. This study proposes a novel approach for the co-disposal and resource utilization of various solid wastes, potentially providing an alternative to clay liner materials for landfills.

Coupled reduction in arsenic methylation and methanogenesis with silicate amendment in arsenic-enriched paddy soils

Methanogens play an important role in the demethylation of arsenic. Soil amendments that inhibit methanogens can increase dimethylarsinic acid (DMA), which is responsible for straighthead disease in rice. A decrease in methanogenesis caused by silicate fertilizer may increase DMA concentration in paddy soils and rice grains; the relationship between these two factors and their impacts on DMA concentration remains unclear. We applied silicate fertilizer (2 Mg ha−1) to japonica and indica rice grown on arsenic-spiked soils and found a simultaneous reduction in methane emissions and pore-water DMA concentration, compared to no-silicate fertilization. Gene and transcript copies of mcrA and arsM, as well as dominant methanogens and arsenic-methylating microbes decreased significantly with silicate fertilization. However, the sulfate-reducing bacteria and the gene and transcript copies of dsrB did not change significantly in response to the application of silicate fertilizer to paddy soils. The abundance of arsenic methylating microbes was significantly and positively correlated with the abundance of methanogens, but not with the abundance of sulfate-reducing bacteria. Methylomonas and Methylobacter, which harbor the arsM gene, were suppressed under silicate fertilization, suggesting that they have the potential to methylate As and play a crucial role in reducing pore-water DMA in As-enriched flooded paddy soils. Increasing Fe concentration, soil pH, and Eh value decreased pore-water DMA concentration, while decreasing arsenite concentration, arsM and mcrA gene abundance decreased it. While silicate fertilization decreased arsenite and DMA concentrations in pore-water, it had no significant effect on rice DMA content, but significantly decreased arsenite content. Results reveal that methanogens and arsenic-methylating microbes have a synergistic relationship under silicate fertilization that facilitates a significant reduction in methane emissions and DMA concentration in As-enriched paddy soils.

Potential amendments of coal fly ash-derived zeolite to beryllium contaminated soil at a legacy waste disposal site

Management of Be contamination using industrial solid waste or solid waste-derived amendments is not well understood. This study investigated the potential of Australian coal fly ash (CFA), derived synthesized zeolite (SynZ) and chitosan-modified zeolite (ModZ), for Be immobilization at the Little Forest Legacy Waste Site (LFLS), a low-level radioactive waste disposal site near Sydney, Australia. In laboratory simulation experiments, the SynZ and ModZ were separately applied as an amendment to both naturally contaminated soil and simulated contaminated (spiked) soil. Different techniques, including pore water (PW), batch desorption, and microbial activities were assessed to provide insight into immobilization mechanisms. Results revealed that amendment of 2% ModZ in soils, substantially decreased Be concentrations in PW (PWBe) ranging from 13.3% to 99.5% across all concentrations of Be. In contrast, PWBe increased while using SynZ, which could be attributed to the increased solubility of different organic-inorganic elements in PW. Moreover, batch desorption using Milli-Q water, simulated acid rainwater [H2SO4/HNO3 = 60/40, (v/v), and 0.11 M acetic acid solution also revealed similar patterns of Be immobilization as found in PWBe analysis. Soil amendments boosted microbial biomass carbon, and phosphorous (MBC,P), along with basal respiration (BRCO2). This indicates increased microbial activities, which are linked with environmental eco-friendliness. This effect was substantially noticed in ModZ-amended soils, exhibiting up to 22 times higher in BRCO2 values compared to unamended soil. Additionally, reduced PWBe was correlated with soluble organic-inorganic elements, desorbed Be in the batch study, and soil MBc. The differences in behavior between SynZ and ModZ underline the importance of carefully studying the various potential amendment materials and the need to evaluate their performance before application in field situations. This study highlights ModZ's effectiveness in eco-friendly Be immobilization, underlining the role of organic functional groups in zeolite architecture, a key factor in controlling Be in soils.

Influence of earthworms on the mobility and bioavailability of metals, metalloids and radionuclides in historically contaminated soil

While soil characteristics such as pH, cation exchange capacity and organic matter are known to influence the mobility of pollutants in soil and the transfer to vegetation, far less attention has been paid to the possible non-trophic influence of organisms on pollutant transfer to other species. When pollutants are present in a bound unavailable form in the mineral or organic fraction, they can be made available through bio-weathering and decomposition of organic material. Within this study, the impact of earthworms on the mobility of metal(loid)s and radionuclides in soil and their transfer to vegetation was evaluated and the pathways through which earthworms work were studied. Soil from a Belgian field, historically contaminated with metal(loid)s and radionuclides, was used and microcosm systems were applied to mimic the natural interactions between soil, earthworms (Lumbricus terrestris) and vegetation (Lolium perenne). Metal and radionuclide concentrations were determined in soil, pore water and grass. In addition, soil pH, (chromophoric) dissolved organic matter, the ionic composition of pore water and the soil microbial activity were analysed. In general, earthworm presence significantly increased the concentration of most pollutants in soil pore water. This could be a direct consequence of decreased soil pH and increased humification. The latter also lead to higher nutrient concentrations in pore water that were depleted in the root zone due to high accumulation by plants. Indications were found for earthworm-induced effects on the soil microbial activity. The results show that earthworm activity can increase leaching of metal(loid)s and radionuclides and enhance dispersion into the environment and transfer to other biota and the food chain. Biologically induced release or remobilization of pollutants in the soil should therefore be considered in the context of risk assessment and site management strategies.

Does higher ratio of wheat straw addition decrease PAHs degradation in PAHs-contaminated paddy soils and PAHs concentrations in rice?

There are considerable studies focusing on impacts of straw returning on PAHs degradation and bioavailability in PAHs-contaminated upland soils, while similar research in paddy soils is limited. Incubation experiments and pot trials were conducted to study effects of straw returning on PAHs degradation in paddy soils and PAHs accumulation in rice, respectively. There are threshold effects of straw returning on PAHs degradation in PAHs-contaminated paddy soils. The inflection point of PAHs degrading was recorded under 0.8 % wheat straw treatment (conventional (CS) and pretreated wheat straw (PS)), which increased PAHs degradation by 18.13–32.36 %. The lowest PAHs concentrations in rice were recorded under 1 % straw (CS and PS) treatment, which was attributed to the highest PAHs degradation in rhizosphere soils. Compared to CS treatment, PS treatment significantly (p < 0.05) increased PAHs degradation by 7.93–10.28 % and PAHs concentrations in rice by 12.38–45.87 % due to that increasing dissolved organic carbon (DOC) enhanced PAHs concentrations in porewater of rhizosphere soils. Higher diversity enhanced the metabolic pathways and function genes to degrade PAHs by improving bacterial phenotypes and biochemical processes under 1 % wheat straw and PS treatment. The present study firstly demonstrated that the effects of straw returning on PAHs degradation in PAHs-contaminated paddy soils and PAHs concentrations in rice depended on amount and methods of straw returning.

The Role of Benthic Fluxes in Acidifying the Bottom Waters in the Northern Gulf of Mexico Hypoxic Zone Based on an Updated Water Column Biogeochemical‐Seabed Diagenetic and Sediment Transport Model

AbstractThe seabed and the water column are tightly coupled in shallow coastal environments. Numerical models of seabed‐water interaction provide an alternative to observational studies that require concurrent measurements in both compartments, which are hard to obtain and rarely available. Here, we present a coupled model that includes water column biogeochemistry, seabed diagenesis, sediment transport and hydrodynamics. Our model includes realistic representations of biogeochemical reactions in both seabed and water column, and fluxes at their interface. The model was built on algorithms for seabed‐water exchange in the Regional Ocean Modeling System and expanded to include carbonate chemistry in seabed. The updated model was tested for two sites where benthic flux and porewater concentration measurements were available in the northern Gulf of Mexico hypoxic zone. The calibrated model reproduced the porewater concentration‐depth profiles and benthic fluxes of O2, dissolved inorganic carbon (DIC), TAlk, NO3 and NH4. We used the calibrated model to explore the role of benthic fluxes in acidifying bottom water during fair weather and resuspension periods. Under fair weather conditions, model results indicated that bio‐diffusion in sediment, labile material input and sediment porosity have a large control on the importance of benthic flux to bottom water acidification. During resuspension, the model indicated that bottom water acidification would be enhanced due to the sharp increase of the DIC/TAlk ratio of benthic fluxes. To conclude, our model reproduced the seabed‐water column exchange of biologically important solutes and can be used for quantifying the role of benthic fluxes in driving bottom water acidification over continental shelves.

Migration and transformation mechanisms of iron and manganese during river infiltration affected by the changes in riverbed sediment thickness

Riverbed scouring and siltation, affected by variations in river flow and sediment concentration, can cause changes in the sediment thickness, leading to the complex feedback between riverbed permeability and nutrient–reactive transport processes. Currently, the migration and transformation of iron and manganese under changed riverbed sediment thickness have not been taken into account. Based on indoor one-dimensional soil column simulation experiments, along with in-situ monitoring, Rhizon pore water sampling, and 16 s rRNA high-throughput sequencing technologies, this study revealed the migration and transformation patterns of iron and manganese in the river infiltration zone and their contribution rates under different sediment thickness conditions. The results demonstrated that as the riverbed sediment thickness increased, the river infiltration rate and sediment permeability coefficient demonstrated a significant decrease over time. For instance, a 5 cm sediment thickness can decrease the sediment permeability coefficient by 30 % within 32 d of infiltration, expand the disconnection zone to 25 cm, narrow the oxidation–reduction zone, and cause the iron and manganese reduction zone to evolve from a single peak to a double peak pattern. Additionally, as the sediment thickness increased, the contribution of organic matter bound iron-manganese oxidation and iron-manganese oxide reduction to Mn2+ and Fe2+ concentrations in sediment pore water decreased, while the contribution of adsorption and complexation-precipitation increased. This study holds great significance for ensuring the safety of drinking water supply and promoting the sustainable utilization of groundwater resources.

Enhanced phosphorus removal from anoxic water using oxygen-carrying iron-rich biochar: Combined roles of adsorption and keystone taxa

Anthropogenic enrichment of phosphorus (P) in water environment can cause eutrophication, harmful algal blooms, and water quality deterioration. Adsorbents are often used for the removal and recovery of P from water, however, P is highly susceptible to re-release in anoxic benthic environments. As a response, this study prepared oxygen-carrying iron-rich biochar (O-Fe-BC) as an effective oxygen micro-nanobubble carrier (Q = 8.7024 cm³/g STP at 1.5 MPa) and P adsorbent (qm = 16.7097 mg P/g, q0.1 = 3.1974 mg P/g). Over the 90-day experimental period with O-Fe-BC, dissolved oxygen (DO) levels in the overlying water could maintain at ∼4 mg/L (peaking at ∼9.5 mg/L), and total phosphorus (TP) and soluble reactive phosphorus (SRP) levels decreased by over 96 %. The higher inorganic phosphorus content in the surface sediment-biochar mixture, along with the lower labile P and Fe concentration in the sediment pore water in the O-Fe-BC group compared to other groups, suggested the enhanced P immobilization. Further mechanism exploration revealed the combined roles of adsorption and microbial response, in which O-Fe-BC achieved efficient phosphate adsorption primarily through inner-sphere complexation via ligand exchange and keystone taxa (particularly Candidatus Electronema) played a crucial role in driving water chemistry divergence. Specially, these cable bacteria could provide large pools of Fe oxides in the surface sediment, binding with P to prevent its release, as supported by significant correlations between Ca. Electronema abundance and oxidation–reduction potential (ORP), TP, SRP, and sediment Fe-P variations. Additionally, a pot experiment with mung bean seedlings showed that the recovered O-Fe-BC significantly promoted the seed germination and growth, indicating its potential as a novel material for removing and recovering P from eutrophic waters. Taken together, our work provided a promising strategy for sustainable anoxia and P pollution mitigation, and also highlighted the indispensable roles of inner-sphere adsorption in P recovery and microbial keystone taxa in P cycling regulation.

A landscape limnology approach to assessing controls on soluble reactive phosphorus in sediment porewater and internal loading risk

Sediment nutrients can be mobilized to overlying water via internal loading, which can be important to aquatic productivity. Using data from 143 Canadian lakes, we show high (~2400-fold) variation of soluble reactive phosphorus (SRP) concentrations in surficial sediment porewater, with results suggesting internal phosphorus loading (IPL) is also likely to vary widely. Consistent with past work at smaller scales, we show that lake depth, pH, trophic status, and bulk sediment Al:P and Fe:P influence porewater SRP, and IPL. Median porewater SRP concentration in lakes with high Al:P (molar ratios >10) were 4.8-fold smaller than in lakes with lower Al:P. In lakes where bulk sedimentary Fe:P molar ratios were >10 porewater SRP was 3.9-fold lower than in lakes with lower Fe:P. High pH (>7.8), along with hyper-eutrophic lakes were associated with higher porewater SRP. Finally, shallow lakes (<4 m depth) had median porewater SRP concentration 6-fold higher than deep lakes (>9 m depth). Important regional differences emerged, linked to regional variation in pH, soils, lake depth and trophic status, and paralleling areas of poor water quality. For example, median porewater SRP in lakes from the Boreal Plains and Prairies ecozones (dominated by Chernozems/Mollisols) was 64-fold and 44-fold higher than in the Boreal Shield (dominated by Podzols/Spodosols) (respectively), although we note that IPL risk is likely important across many ecozones. Using national data, we found in-lake measurements (particularly pH, and salinity) showed strong capacity in predicting porewater SRP (explaining 60–72 % of the variance in the data). Importantly, watershed predictors showed good predictive power, explaining ~50 % of variance in porewater SRP using variables including soil types, and % agriculture. Porewater SRP can be predicted with reasonable accuracy using easily measured variables, as can estimates of internal phosphorus loading, suggesting that landscape limnology holds strong potential in helping to inform lake management by informing understanding of in-lake nutrient sources.

Rhamnolipids Enhance Bioremediation of Petroleum-Contaminated Soil

_ This article, written by JPT Technology Editor Chris Carpenter, contains highlights of paper SPE 215952, “Enhancing Bioremediation of Petroleum-Contaminated Soil Using Rhamnolipids: A Combined Laboratory and Field Study,” by Pan Ni, Lehigh University; Yonglin Ren, SPE, Stepan Oilfield Solutions; and Derick G. Brown, Lehigh University, et al. The paper has not been peer reviewed. _ Hydrocarbon spills can occur at various stages of the oil and gas exploration and production process. Treating these spills onsite to avoid more-expensive excavation and incineration processes would be beneficial. The study outlined in the complete paper aims to optimize the use of rhamnolipid biosurfactants for enhancing the bioremediation of hydrocarbon-contaminated soil. The goal of this work was to explore the effects of rhamnolipid application on hydrocarbon degradation rate under both laboratory and field conditions and to examine the effects of this treatment on the indigenous soil microorganism population. Introduction The authors write that, to the best of their knowledge, previous research studies on rhamnolipid-based soil remediation focused on either laboratory or field tests and that comparison between laboratory-scale and field-scale tests is overlooked but necessary for practical applications. Materials and Methods Materials and Chemicals. The soil used for this work (23 kg for the laboratory test, 10 metric tons for the field test) was obtained from a contaminated site in Longford Mills, Canada. The soil properties are presented in Table 1 of the complete paper. The rhamnolipid stock solution featured 9.8 wt% rhamnolipid blends in deionized water. Another commercial remediation agent (enzyme-based) was used in the field test to compare with the performance of rhamnolipid. Ammonium chloride (NH4Cl) and potassium hydrogen phosphate (K2HPO4) also were used along with sodium hydroxide (NaOH). Experimental Setup. Both laboratory and field tests were ex-situ tests using simulated soil piles. The laboratory test was conducted for 193 days. For the laboratory experiments, an aerobic/anaerobic respirometer system equipped with a low-temperature incubator was used to monitor the in-situ oxygen uptake inside eight reactors (Fig. 1). Each reactor contained 250 g of soil with rhamnolipid doses of 0, 0.1, 0.5, and 1 g/kg. The temperature was set to 25°C. Inside each reactor was placed 10 mL of 4-M NaOH in a 20-mL glass beaker to adsorb the produced CO2. A parallel set of eight reactors was prepared and operated under the same conditions. The nutrients of nitrogen and phosphorous (NH4Cl and K2HPO4) were added at specific times based on the oxygen uptake rate monitored by the respirometer. To avoid the possible inhibition of the microbes in the soil as a result of high ionic strength (greater than 160 mM) in the soil pore water, NH4Cl and K2HPO4 were added so that the molar concentration in the soil pore water did not exceed 100 mM. The field test is being conducted in Longford Mills, Ontario, Canada, and is ongoing at the time of writing. For the field test, 10 metric tons of soil were mixed to achieve homogeneity before the preparation of the soil piles. Five different treatment conditions were examined using duplicate soil piles (10 piles total), with each consisting of 1 metric ton of soil. Nutrient addition was similar to that used in the laboratory tests. Temperature and moisture were monitored every few days at five points in each soil pile, and the pH was monitored once every month at five points.