Pore Water Extraction Research Articles

Groundwater level effects on greenhouse gas emissions from undisturbed peat cores

Peat soils store a large part of the global soil carbon stock, which can potentially be lost when they are drained and taken into cultivation, resulting in CO2 emission and land subsidence. Groundwater level (GWL) management has been proposed to mitigate peat oxidation, but may lead to increased emissions of nitrous oxide (N2O) and methane (CH4).The aim of this experiment was to study trade-offs between greenhouse gas emissions from peat soils as a function of GWL. We incubated 1 m deep, 24 cm diameter undisturbed bare soil cores, after removal of the grass layer, from three contrasting Dutch grassland peat sites for 370 days at 16 °C. The cores were subjected to drying-wetting cycles, with the GWL varying between near the soil surface to 160 cm below the surface. We measured gas fluxes of CO2, N2O and CH4 from the soil surface, extracted pore water for DOC and mineral nitrogen analysis, and measured soil hydraulic and shrinkage characteristics.Emissions of CO2 increased after lowering the GWL, but showed different GWL-response curves during rewetting of the soil. On average, highest CO2 emissions of 1.5 g C·m−2 day−1 were found at a GWL of 80 cm below the surface. However, the 0 cm GWL was the only treatment with significantly lower CO2 emissions than other GWLs. Cumulative CO2 emissions differed significantly between sampling sites. Emissions of N2O showed a different response, peaking at GWL heights above −20 cm, particularly after a recent GWL rise. Though not significantly different, the highest N2O emissions were measured at the 0 cm GWL treatment. We confirmed this pattern for N2O in un-replicated soil cores with grass sward, although emission values were lower in these cores due to the root uptake of mineral nitrogen. CH4 emissions or −uptake remained low under any GWL. We conclude that raising the GWL is a successful strategy to reduce CO2 emissions from peat oxidation. However, raising the GWL close to the soil surface could lead to N2O emissions that negate any gains in terms of global warming potential. Our results suggest that raising the GWL in peat grasslands to −20 cm creates such a risk. A constant GWL at the surface (0 cm) would be preferential for mitigating both CO2 and N2O emissions, although such conditions don’t allow for agricultural grass production (mowing or grazing).

Accounting for the impact of tree size and soil spatial variability on leaching from orchards

Commercial agricultural production of orchards is based on water and fertilizer applications. Over-application and orchard spatial variability lead to water and nitrogen (N) losses through leaching and environmental damage. This work introduces a novel advanced method to quantify N and water leaching at the orchard scale by combining soil monitoring, unmanned aerial vehicle (UAV) imagery to estimate tree size, leaf N and canopy content, and water flow and N transport models. Four neighboring commercial orange orchards were selected, and 48 representative trees were instrumented with suction cups and tensiometers at a depth of 90 cm. The physical properties of the soil profiles in the vicinity of each tree were determined. During 2019–2021, UAV structure-from-motion (SfM) photogrammetry was used to classify the tree sizes into small, medium, and big categories. Soil porewater extraction and soil matric potential measurements were conducted every three weeks, while leaf N contents (LNC) were determined through bimonthly leaf tissue sampling. The LNC, N leaching, soil water state, and N use efficiency (NUE) (the ratio between the mass of plant N uptake and the mass of N applied per area) were strongly related to tree size classification. Results of the calibrated hydrological model illustrated that the 'big' trees exhibited minimal N leaching due to higher transpiration compared to the other tree size categories. An NUE map was established using the calibrated model and field measurements, demonstrating that soil spatial variability minimally affected N leaching compared to tree size distribution. The presented holistic approach can be used to identify N-leaching hotspots, improve orchard scale NUE estimates, and promote sustainable agricultural management practices.

Seawater contamination by coring and pore water sampling of marine sediments

Coring of sediments with minimal physical disturbance, and sampling of pore water with minimal contamination from seawater, are critical in marine geochemistry and microbiology. Yet, sediment coring generally causes smearing of sediment down along the inside of the core liner and leaves seawater and fluid mud trapped around the core. This seawater is a source of diffusive or advective exchange of solutes with the core, which affects the chemistry of retrieved pore water. The exchange depends on the time elapsed between coring and the end of pore water extraction. The degree of seawater contamination is difficult to determine and has generally been neglected in the geochemical literature. Yet, it is possible to quantify seawater contamination due to the high millimolar concentration of sulfate in seawater and low micromolar concentration in the subsurface methanic zone, where sulfate is largely depleted. Analysis of 540 sediment cores from a global database showed that sulfate concentration data beneath the sulfate-methane transition were often truncated and stated as “0” or “0,0” mM, thereby preventing an evaluation of seawater contamination. Among the 181 sediment cores for which the mM sulfate concentrations were reported with two or three decimal places, concentrations measured in methanic sediments were up to an order of magnitude higher than the estimated in situ concentrations in gravity cores and two orders of magnitude higher in cores recovered by scientific ocean drilling. A comparison between pore water extraction by Rhizon suction samplers and by high-pressure squeezers in cores from Baltic Sea Expedition 347 of the IODP (International Ocean Discovery Program) showed no systematic difference in the degree of contamination. A comparison with a perfluorocarbon (PFC) tracer injected by IODP coring into the drilling fluid showed a seawater contamination similar to that based on sulfate in the methanic zone. In IODP cores, where the true in situ sulfate concentration is generally unknown, we calculated the theoretical sulfate concentration that corresponded to equilibrium between SO42−, Ba2+ and barite (BaSO4) to show that the equilibrium sulfate concentrations in the methanic zone are much lower than the sulfate concentrations measured in pore water samples, again indicating seawater contamination. We used a time-resolved diffusion model to calculate how contaminating seawater ions penetrate from the external liner fluid into sediment cores before pore water is extracted. We conclude that nearly all published pore water samples retrieved from subsurface sediments are contaminated by seawater to some degree. We also conclude that sensitive sulfate analyses in methanic sediments constitute a unique opportunity to quantify this contamination and thereby provide a better possibility to control it.

Revisiting the applicability and constraints of molybdenum- and uranium-based paleo redox proxies: comparing two contrasting sill fjords

Abstract. Sedimentary molybdenum (Mo) and uranium (U) enrichments are often used as redox proxies to reconstruct bottom water redox changes. However, these redox proxies may not be equally reliable across a range of coastal settings due to varying depositional environments. Fjords vary greatly in their depositional conditions, due to their unique bathymetry and hydrography, and are highly vulnerable to anthropogenic and climatic pressures. Currently, it is unknown to what extent Mo and U sequestration is affected by variable depositional conditions in fjords. Here, we use pore water and sequential extraction data to investigate Mo and U enrichment pathways in sediments of two sill fjords on the Swedish west coast with contrasting depositional environments and bottom water redox conditions. Our data suggest that sedimentary authigenic Mo and U pools differ between the two fjords. At the (ir)regularly dysoxic (oxygen = 0.2–2 mL L−1) Gullmar Fjord, authigenic Mo largely binds to manganese (Mn) oxides and to a lesser extent to iron (Fe) oxides; Mo sulfides do not play a major role due to low sulfate reduction rates, which limits the rate of Mo burial. Authigenic U largely resides in carbonates. At the (ir)regularly euxinic (oxygen = 0 mL L−1; total hydrogen sulfide ≥ 0 mL L−1) Koljö Fjord, authigenic Mo is significantly higher due to binding with more refractory organic matter complexes and Mo-Fe-sulfide phases. Uranium is moderately enriched and largely bound to organic matter. We found no direct evidence for temporal changes in bottom water redox conditions reflected in Mo and U enrichments at either Gullmar Fjord or Koljö Fjord. While sulfidic bottom waters favor Mo sequestration at Koljö Fjord, enrichment maxima reflect a combination of depositional conditions rather than short-term low-oxygen events. Our data demonstrate that secondary pre- and post-depositional factors control Mo and U sequestration in fjords to such an extent that bottom water redox conditions are either not being systematically recorded or overprinted. This explains the large variability in trace metal enrichments observed in fjords and has implications for applying Mo and U as proxies for environmental redox reconstructions in such systems.

Porewater profiles of Cl and Br in boreholes penetrating the Mesozoic sequence in northern Switzerland

The analysis of tracer profiles of porewaters is a valuable tool to understand transport processes in argillaceous rocks and to unravel the paleo-hydrogeology of a site. In this contribution, anionic tracers (Cl, Br) from eight boreholes located in three study areas (∼20 km apart) penetrating the ∼800 m thick Mesozoic sequence in northern Switzerland, were analysed. A specific focus was on the Opalinus Clay, a ∼100 m thick homogeneous claystone formation, foreseen as host rock for radioactive waste disposal in Switzerland, as well as its mostly clay-rich confining units. Using porewater extraction methods, such as high-pressure squeezing, advective displacement and aqueous extraction, a unique dataset of spatially highly resolved Cl and Br profiles could be obtained. These show systematic and comparable patterns suggesting common paleo-hydrogeological evolution paths for all three study areas. The scatter in the tracer profiles based on the aqueous extraction data are mostly related to the uncertainty in the estimation of the anion-accessible porosity fraction on one hand and in the water content data in the case of low-porosity calcareous rocks on the other. Differences between the study areas are in line with differences in aquifer characteristics. The current shape of the anion profiles is dominated by diffusive exchange with the bounding aquifers over the last several ten thousands to millions of years, as supported by numerical modelling. The Br/Cl signals also suggest the preservation of older signals related to halite dissolution and highly evolved evaporitic porewaters occurring in evaporite-bearing units of the Triassic. Overall, the adopted methodology has enabled to obtain a unique dataset of anionic tracers at regional scale providing a solid basis for understanding the regional paleo-hydrogeology of siting areas for a potential nuclear waste repository.

Pore water pressure maintaining sampler for deployment on deep-sea ROV-Jellyfish

Obtaining high-quality pore water samples is of great importance for marine resource investigations. We describe a deep-sea in-situ pore-water pressure-maintaining sampler aboard the heavy-duty ROV-Jellyfish. It can operate at water depths up to 3000 m and acquire 24 different pore-water pressure-holding samples of seafloor sediments with a sampling depth resolution of 2 cm. In this study, the working capacity of the pore water sampler is initially analyzed through structural design and theoretical calculation. The force changes of the integrated system of sampling Rhizons during the penetration of sediments and the extraction of pore water were simulated by the CEL-coupled Euler method in ABAQUS to determine the material and working speed of the integrated system.Meanwhile, the interaction and diffusion effects at the interface between the sample and deionized water during the pore water sample storage under pressure retention were investigated by the laminar flow and dilute matter diffusion methods in COMSOL. Laboratory experiments were conducted to analyze the effect of 2 cm depth resolution on the maximum sampling volume when obtaining pore water samples at different depths during the sampling process, thus reducing the mutual contamination between pore water samples from adjacent layers. Finally, the sea trials prove the sampler's pressure-holding sealing performance and application performance. Thus, the pore water sampler can carry out more in-depth scientific applications.

Technical note: Testing the effect of different pumping rates on pore-water sampling for ions, stable isotopes, and gas concentrations in the hyporheic zone

Abstract. The hyporheic zone (HZ) is of major importance for carbon and nutrient cycling as well as for the ecological health of stream ecosystems, but it is also a hot spot of greenhouse gas production. Biogeochemical observations in this ecotone are complicated by a very high spatial heterogeneity and temporal dynamics. It is especially difficult to monitor changes in gas concentrations over time because this requires pore-water extraction, which may negatively affect the quality of gas analyses through gas losses or other sampling artifacts. In this field study, we wanted to test the effect of different pumping rates on gas measurements and installed Rhizon samplers for repeated pore-water extraction in the HZ of a small stream. Pore-water sampling at different pumping rates was combined with an optical sensor unit for in situ measurements of dissolved oxygen and a depth-resolved temperature monitoring system. While Rhizon samplers were found to be highly suitable for pore-water sampling of dissolved solutes, measured gas concentrations, here CH4, showed a strong dependency of the pumping rate during sample extraction, and an isotopic shift in gas samples became evident. This was presumably caused by a different behavior of water and gas phase in the pore space. The manufactured oxygen sensor could locate the oxic–anoxic interface with very high precision. This is ecologically important and allows us to distinguish between aerobic and anaerobic processes. Temperature data could not only be used to estimate vertical hyporheic exchange but also depicted sedimentation and erosion processes. Overall, the combined approach was found to be a promising and effective tool to acquire time-resolved data for the quantification of biogeochemical processes in the HZ with high spatial resolution.

Assessing the activity of mud volcanism using boron isotope ratios in pore water from surface sediments of mud volcanoes off Tanegashima (SW Japan)

Mud volcanoes can cause various geohazards, so it is very important to know their activity level and their distribution. Surface sediments were collected from four submarine mud volcanoes (MVs) off Tanegashima (SW Japan), namely, MV1, MV2, MV3, and MV14. We extracted pore water from the surface sediments and investigated its chemical and isotopic compositions. The sodium (Na) and chloride (Cl-) concentrations decreased and the boron (B) and lithium (Li) concentrations increased with increasing depth, suggesting that some fluids with lower Na and Cl- concentrations and higher B and Li concentrations than seawater were supplied upward from the deep sub-seafloor. The fluid advection velocities estimated from the pore-water profiles differed for each MV, and those of MV3 were the fastest (14 cm/yr) in this study. The estimated equilibrium temperature with clay minerals using Na and Li concentrations were 93-134°C, corresponding to the temperature of environments around 3.7 to 5.3 km below the seafloor. This indicates that these components originated from these depths and that the origin depth did not reach the plate boundary in this area. The B isotope ratio in the pore water was extremely high up to +57 ‰, suggesting that it was strongly affected by adsorption onto the surface of the sediments. A higher B isotope ratio (+57 ‰) was detected in MV3, which was considered to be more active, indicating that more B was adsorbed onto clay minerals supplied from deeper depths.

Two-Dimensional Mapping of Arsenic Concentration and Speciation with Diffusive Equilibrium in Thin-Film Gels.

We present a new approach combining diffusive equilibrium in thin-film gels and spectrophotometric methods to determine the spatial distribution of arsenite, arsenate, and phosphate at submillimeter resolution. The method relies on the simultaneous deployment of three gel probes. Each retrieved gel is exposed to malachite green reagent gels differing in acidity and oxidant addition, leading to green coloration dependent on analyte speciation and concentration. Hyperspectral images of the gels enable mapping the three analytes in the 2.5-20 μM range. This method was applied in a contaminated brook in the Harz mountains, Germany, together with established mapping of dissolved iron. The use of two-dimensional (2D) gel probes was compared to traditional porewater extraction. The gels revealed banded porewater patterns on a mm-scale, which were undetectable using traditional methods. Small-scale correlation analyses of arsenic and iron microstructures in the gels suggested active iron-driven local redox cycling of arsenic. Overall, the results indicate continuous net release of arsenic from contaminant particles and deepen our understanding of arsenate transformation under anaerobic conditions. This study is the first fine-scale 2D characterization of arsenic speciation in porewater and represents a crucial step toward understanding the transfer and redox cycling of arsenic in contaminated sediment/soil ecosystems.

The role of the HADES URL in better understanding of the Boom Clay pore water geochemistry

Abstract When assessing a rock formation for its suitability as a potential host rock for the disposal of radioactive waste, knowledge about its pore water chemical composition is essential. When the HADES underground research laboratory became operational in the early 1980s, it offered the possibility of extracting pore water from Boom Clay. At the time, however, there was almost no experience of sampling pore water from deep clay formations. The low hydraulic conductivity of clays makes it difficult to extract pore water and the sampling process itself can induce changes in the observed chemical characteristics due to oxidation and re-equilibration with the ambient air. In the past decades, significant progress has been made in the techniques and protocols to sample and monitor pore water. The use of nitrogen instead of compressed air to drill boreholes and installing piezometers limited the disturbances induced by oxidation of the clay. Furthermore, an advanced system was developed to simultaneously sample pore water and dissolved gases and measure some key geochemical parameters such as pH, pCO 2 and redox potential under in situ conditions. This has resulted in a more reliable characterization of the Boom Clay pore water and a better understanding of perturbing processes such as oxidation.

Pore solution alkalinity of cement paste as determined by Cold Water Extraction

Cold Water Extraction (CWE) is a technique used to extract the pore solution of cementitious materials and to study its alkalinity. CWE can be used on paste, mortar or concrete, and requires only standard laboratory equipment. The method is not yet standardised, so several parameters must be arbitrarily selected when conducting the test.This work investigated the influence of four parameters on the calculated alkali metal concentrations in the pore solution: the method for determining the amount of pore solution (oven-drying at 40 and 105 °C, desiccator with silica gel and solvent exchange), the size fraction of the powdered material, the leaching duration and the liquid-to-solid ratio. A comparison with values obtained by Pore Water Extraction (PWE) on two cement types emphasises and quantifies the crucial impact of the amount of pore solution on CWE results. The results suggest that some bound alkali metals may be released during CWE. A mechanism is proposed, and recommendations are made to limit any effect of this on CWE results.

Determination of antimicrobial agents and their transformation products in an agricultural water-soil system modified with manure

Manure fertilization is the primary source of veterinary antimicrobials in the water-soil system. The research gap is the fate of antimicrobials after their release into the environment. This study aimed to provide a detailed and multi-faceted examination of fertilized cultivated fields using two types of manure (poultry and bovine) enriched with selected antimicrobials. The research focused on assessing the mobility and stability of antimicrobials in the water-soil system. Additionally, transformation products of antimicrobials in the environment were identified. The extraction (solid-phase extraction and/or solid–liquid extraction) and LC–MS/MS analysis procedures were developed to determine 14 antimicrobials in the soil and pore water samples. Ten out of fourteen antimicrobials were detected in manure-amended soil and pore water samples. The highest concentration in the soil was 109.1 ng g−1 (doxycycline), while in pore water, it was 186.6 ng L−1 (ciprofloxacin). Sixteen transformation products of antimicrobials were identified in the soil and soil-related pore water. The same transformation products were detected in both soil and soil pore water extracts, with significantly higher signal intensities observed in soil extracts than in water. Transformation products were formed in oxidation, carbonylation, and ring-opening reactions.

A method for a fast and economical in situ collection of pore water in sandy sediments

Marine sediment represents one of the most significant carbon reservoirs. Extraction of pore water from the uppermost 10 cm of the sediment column, just below the sediment-water interface, in coastal environments can be used to assess the rapid chemical changes caused by extensive subsurface biological and chemical reactions. However, owing to relatively large grain size of the sediment in some shallow coastal environments, sediment and pore water mixes quickly making collection of core samples for pore water extraction extremely difficult. Here, we present a simple method utilizing Rhizons to collect in situ pore water from coastal environments. We conducted both ex situ and in situ experiments, using fluorescein as a tracer, to understand the influence of overlying water during pore water collection through this method. These experiments also allowed us to assess the volume of pore water collected before fluorescein is observed in the samples at different vertical depths within the sediment column. We found that: 1. discarding the initial 2 mL of water minimizes the memory effect, 2. collection of 10 mL of water avoids interference from surrounding pore water and the overlying water column and 3. a vertical resolution of minimum 2 cm could be attained for sediments with grain size of 1 mm and less. We finally present data from two linear transects from different sites in the Gulf of Aqaba. Results from these case studies demonstrate expected patterns of high concentrations of iron and hydrogen sulfide in pore water from the sediment where surface coloration suggested iron and sulfate reduction was dominating, respectively. Both case studies, therefore, independently validated the Rhizon sampler method for collecting pore water in situ from marine sediments in coastal environments.

Equilibrium Porewater Measurement of PCBs and PAHs Using Direct Water Extraction and Comparison with Passive Sampling.

The freely dissolved concentration of hydrophobic pollutants in sediment porewater (Cpw) is a critical driver for exposure to aquatic organisms, bioaccumulation, toxicity, and flux across interfaces. In this research, we compared direct porewater extraction and passive sampling for Cpw measurements of a range of PCBs and PAHs in field-collected sediments. The direct water extraction method provided accurate quantification of Cpw for low to moderately hydrophobic PCB and PAH compounds (log Kow < 6.5) that compared well with independent measurements performed using four passive sampling methods. Direct water extraction was adequate to assess narcosis toxicity of PAHs to benthic organisms that is driven by the concentrations of low to moderately hydrophobic PAHs (naphthalene to chrysene), even for a hypothetical sediment that had a tenth of the PAH concentrations of the study sediments and was assessed to be nontoxic. Prediction of PCB bioaccumulation in benthic organisms agreed within 50% for all measurement methods, but it was apparent that for less contaminated sediments, the direct water extraction method would likely have detection limit challenges, especially for the strongly hydrophobic PCBs. To address the uncertainty of the Cpw measurement of the strongly hydrophobic compounds and naphthalene, a new extrapolation approach is demonstrated that can be applicable for both direct water extraction and passive sampling methods.

Facilitating maintenance of stormwater ponds: comparison of analytical methods for determination of metal pollution

Stormwater ponds are widely used for controlling runoff quality through the sedimentation of particles and associated pollutants. Their maintenance requires regular removal and disposal of accumulated material. This necessitates an assessment of material hazardousness, including potential hazard due to its contamination by metals. Here we analyze 32 stormwater pond sediment samples from 17 facilities using several chemical analysis methods (total extraction, sequential extraction, diffusive gradients in thin-films DGT, and pore water extraction) in order to consider the complementarity and comparability of the different approaches. No clear relationship was found between analyses that have the potential to measure similar metal fractions (DGT and either fraction 1 of the sequential extraction (adsorbed and exchangeable metals and carbonates) or pore water concentrations). Loss on ignition (LOI) had a significant positive correlation with an indicator of the environmental risk developed in this paper (∑ranks) that incorporates different metals, speciations, and environmental endpoints. Large variations in metal levels were observed between ponds. As clustering was limited between the different analyses, a comprehensive analysis of different parameters is still needed to fully understand metal speciation and bioavailability.

A novel passive sampling and sequential extraction approach to investigate desorption kinetics of emerging organic contaminants at the sediment−water interface

Forms of organic contaminants is an important driver of bioavailable fraction and desorption kinetics of pollutants binding to sediments. To determine fluxes and resupply of nine environmentally-relevant antipsychotic drugs, which are emerging pollutants that can have adverse effects on aquatic organisms, interface passive samplers of diffusive gradients in thin films (DGT) were deployed for 21 days, in situ at the sediment-water interface in submerged sandy riverbank sediments. At each deployment time, samples of sediment were collected and subjected to consecutive extraction of pore water, as well as rapidly-desorbing (labile), stable-desorbing, and bound residue fractions. Concentrations of antipsychotic drugs decreased with sediment depth with the greatest concentrations observed in the top 2 cm. Positive fluxes of antipsychotic drugs were observed from sediment to surface water. The dynamic fraction transfer model indicated that the labile fraction can be resupplied with a lag time (> 21 d). When results were further interpreted using the DGT-induced fluxes in soils and sediments (DIFS) model, partial resupply of antipsychotic drugs from sediment particles to porewater was demonstrated. Desorption occurred within the entirety of the observed 15 cm depth of sediment. Fastest rates of resupply were found for carbamazepine and lamotrigine. Size of the labile pool estimated by the DIFS model did not fully explain the observed resupply, while a first-order three-compartment kinetic model for the fast-desorbing fraction can be used to supplement DIFS predictions with estimations of labile pool size.

Estimating the bioavailability of acetochlor to wheat using in situ pore water and passive sampling

The intensive use of acetochlor in China leads to its extensive existence in soil which may result in contamination of crops and commodities. Therefore, it is vital to assess the bioavailability and phytotoxicity of acetochlor to crops. In this study, four measurements involved in in situ pore water extraction (CIPW), passive sampling extraction (Cfree), ex situ pore water extraction (CEPW), and organic solvent extraction (Csoil) were conducted to assess the bioavailability and phytotoxicity of acetochlor to wheat plant plants in five soils. The results showed that the acetochlor concentrations accumulated in wheat foliage and roots were in the range of 0.11–0.87 mg/kg and 0.09–2.02 mg/kg in the five tested soils, respectively, and had a significant correlation with the acetochlor values analyzed by CIPW (R2 = 0.83–0.90, p < 0.0001) or the Cfree method (R2 = 0.86–0.92, p < 0.0001). The acetochlor concentrations in the five soils measured by these two methods were also correlated with the IC50 values of acetochlor in wheat foliage and roots (R2 > 0.69, p ≤ 0.05). The results indicated that the CIPW and Cfree methods were effective in evaluating acetochlor toxicity to wheat and the acetochlor concentrations in wheat. The effects of soil physical and chemical properties including pH, organic matter content (OMC), clay content, and cation exchange capacity (CEC) on the acetochlor toxicity to wheat were analyzed, and soil OMC was found to be the dominant factor affecting the toxicity of acetochlor in the soil-wheat system.

Influence of equilibration time, soil texture, and saturation on the accuracy of porewater water isotope assays using the direct H2O(liquid)–H2O(vapor) equilibration method

The hydrogen and oxygen stable isotopes of water (δ2H and δ18O) are powerful tracers for studying subsurface water flow processes, but the extraction of porewater from unsaturated soil is complex and laborious. The direct liquid–vapor equilibration method (DLVE) for isotope analysis overcomes this challenge by analyzing headspace vapor in isotopic equilibrium with the porewater under closed system conditions. However, the effect of the equilibration time, soil texture, and porewater saturation on isotopic results is not fully understood yet. We tested three differently textured, disaggregated soils (sandy, silty loam and clay) to assess how the equilibration time is impacted by (i) porewater saturation (100%, 80%, 60%, and 40%), and (ii) soil surface area. For all tests, the water loss through diffusion was negligible (<0.3%). The experiments showed that for disaggregated sandy soil, 24 h was a sufficient isotopic equilibration time regardless of water saturation level. Similarly, 24 h was sufficient for kaolinite samples with 100% saturation exhibiting little isotopic variance even after 168 h of equilibration. For saturated silty loam with 2% organic carbon content, 96 h was the optimal equilibration time, whereas saturated silty loam with 4% organic carbon content did not reach isotopic equilibrium by 168 h. The optimal equilibration time increased depending on whether soil samples were disaggregated or kept in a core cutter. Inconclusive results for silty soils with organic carbon revealed the need to further investigate the possible influence of organic carbon on the DLVE method.

Enantioselectivity of new chiral triazole fungicide mefentrifluconazole: Bioactivity against phytopathogen, and acute toxicity and bioaccumulation in earthworm (Eisenia fetida)

Elaborating the environmental behavior of mefentrifluconazole, a novel triazole fungicide, in stereoselective level is of paramount importance for the application of the pesticide in agriculture. In this study, the enantioselective bioactivity, acute toxicity and stereoselective bioaccumulation of mefentrifluconazole in earthworm (Eisenia fetida) were investigated. Bioactivity tests against four pathogens revealed that R-(−)-mefentrifluconazole exhibited approximately 11–113 times higher bioactivity than its S-(+)-mefentrifluconazole. However, the LC50 of S-(+)-, rac- and R-(−)-mefentrifluconazole to earthworm was measured to be 4.1, 11.4 and 7.3 μg/cm2, respectively, indicating active ingredient R-(−)-mefentrifluconazole is less toxic than its racemate and S-form. Accumulation of mefentrifluconazole in earthworms was non-enantioselective and negatively related to its adsorption onto soils. The concentration of mefentrifluconazole in in situ pore water (CIPW) and CaCl2 extraction (CCaCl2) was closely related to its accumulation in earthworms, suggesting that CIPW and CCaCl2 could be appropriate indicators for estimation of the bioavailability of mefentrifluconazole in soil. Conclusively, our study provides necessary information for the risk assessment of mefentrifluconazole in agriculture.

Collection and use of porewater data from sediment bioassay studies for understanding exposure to bioavailable metals.

The US Environmental Protection Agency Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms: Metal Mixtures (Cadmium, Copper, Lead, Nickel, Silver and Zinc) equilibrium partitioning approach causally link metal concentrations and toxicological effects; they apply to sediment and porewater (i.e., interstitial water). The evaluation of bioavailable metal concentrations in porewater, using tools such as the biotic ligand model, provides an advancement that complements sediment-based evaluations. However, porewater characterization is less commonly performed in sediment bioassays than sediment chemistry characterization due to the difficulty and expense of porewater collection as well as concerns about interpretation of porewater data. This study discusses the advantages and disadvantages of different porewater extraction methods for analysis of metals and bioavailability parameters during laboratory sediment bioassays, with a focus on peepers and centrifugation. The purpose is to provide recommendations to generate bioassay porewater data of sufficient quality for use in risk-based decision-making, such as for regulated cleanup actions. Comparisons of paired data from previous bioassay studies indicate that metal porewater concentrations collected via centrifugation tend to be higher than those collected via peepers. However, centrifugation disrupts the redox status of the sediment; also, metal concentrations can vary markedly based on centrifugation conditions. Data to compare the concentrations of peeper- and centrifugation-collected bioavailability parameters (e.g., major ions, pH) are much more limited, but indicate smaller differences than those observed for metal concentrations. While peepers can be sampled without altering the redox status of the porewater, the small volume of porewater peepers collected is enough for metal concentration analysis, but insufficient for analysis of all metal bioavailability parameters. Given the benefits of metal collection via peepers, it is optimal to use centrifugation and peepers in tandem for bioassay porewater collection to improve bioavailability predictions. Environ Assess Manag 2022;18:1321-1334. © 2021 SETAC.