The challenge in measuring low-permeability materials: a comparison of different approaches

The German repository site selection procedure calls for a radioactive waste containment zone with a low-permeability host rock (kf<10-10 m s−1, StandAG §23, 5) and long-term sealing by barrier materials (EndlSiAnfV, 2020; ESK, 2019). The potential host rocks, clay and rock salt, as well as the considered barrier materials, bentonite and compacted crushed salt, show permeability in the range of kf∼10-16 m s−1 (K∼10-21 m2). These low values suggest that advective flow is as slow as diffusive mass flux. Measuring such low permeability with adequate accuracy challenges measurement setups and respective error evaluation. Methodologies. Several low-permeability measurements are carried out by transient tests, e.g. by monitoring controlled fluid pressure changes in: (1) pressure decay and (2) oscillating pulse tests. The first method (1) deviates permeability from the time needed to compensate pressure differences through the sample. The latter (2) monitors phase shift and amplitude attenuation of controlled pressure pulses passing through the sample. Any permeability measurement needs to be post-processed, e.g. for: (1) material-intrinsic controls (saturation state, storativity, the fluids' compressibility, etc.), (2) environmental controls (temperature, confining pressures, etc.) and (3) theoretical considerations (Klinkenberg correction, multi-phase wetting angles, etc.). Salts. A porosity-permeability relation was found down to K=10-19 m2 (e.g., Popp et al., 2007). Testing fluids were NaCl brine, oils, He and N2 as a fluid. As a matter of current research, a critical, low-permeability value might be associated with the so-called “percolation threshold” that defines the minimal requirements for an interconnected pore system (e.g., DAEF, 2016). Clays. A major challenge is the long duration of sample saturation (up to several months) and pressure equilibration (often days), as well as precise, temperature-compensated measuring and the determination of the samples' storativity (e.g., Winhausen et al., 2021). Testing fluids are commonly designed mixtures mimicking the rocks' pore waters. Geotechnical barrier materials. The permeability testing performed is similar to that of salt and clays mentioned above. However, both barrier materials, crushed salt and bentonite, have significant permeability early after emplacement. This is beneficial, as it allows the outflow of unwanted canister corrosion gases. Eventually, the permeability drops by orders of magnitude and the barriers become tight seals in the long-term. Here, identifying the gas entry/breakthrough pressure has been valuable (e.g., Rothfuchs et al., 2007). Figure 1 shows a preliminary sensitivity analysis as an example of pressure decay measurements. It suggests that the pressure equilibration term (c), and hence the test duration, is most sensitive to the calculation of low permeability. However, the large variation of (representative) material and environmental controls make permeability measurements complex. This workshop aims to encourage discussions on uncertainty and sensitivity of the influencing controls, such that it may lead to a “best-practice” guide for permeability measurements.

Microbial activity, methane production, and carbon storage in Early Holocene North Sea peats

Northern latitude peatlands act as important carbon sources and sinks, but little is known about the greenhouse gas (GHG) budgets of peatlands that were submerged beneath the North Sea during the last glacial–interglacial transition. We found that whilst peat formation was diachronous, commencing between 13 680 and 8360 calibrated years before the present, stratigraphic layering and local vegetation succession were consistent across a large study area. Large carbon stores were measured. In situ methane (CH4) concentrations of sediment pore waters were widespread but low at most sites, with the exception of two locations. Incubation experiments in the laboratory revealed molecular signatures of methanogenic archaea, with strong increases in rates of activity upon methylated substrate amendment. Remarkably, methanotrophic activity and the respective diagnostic molecular signatures could not be detected. Heterotrophic Bathyarchaeota dominated the archaeal communities, and bacterial populations were dominated by candidate phylum JS1 bacteria. In the absence of active methanogenic microorganisms, we conclude that these sediment harbour low concentrations of widespread millennia-old CH4. The presence of large widespread stores of carbon and in situ methanogenic microorganisms, in the absence of methanotrophic microorganisms, holds the potential for microbial CH4 production if catalysed by a change in environmental conditions.

Assessment of concentration and distribution of total mercury and polychlorinated biphenyls in Green Bay, Wisconsin, USA

Under the 1987 Great Lakes Water Quality Agreement, the lower Green Bay and Fox River estuary have been labeled as areas of concern due to the contamination of mercury and polychlorinated biphenyls (PCBs) from industrialization. These pollutants pose substantial health and environmental hazards for the Green Bay region. The PCBs reported in this region, including Aroclor 1242, are known to trigger carcinogenic responses in animals and mercury targets the central nervous system and vital organs. Furthermore, these compounds are extremely difficult to remove from the environment once introduced. Extensive remedial actions have been implemented including dredging sediments in the Lower Fox River from DePere to Green Bay. The purpose of this study is to assess the concentration and distribution of Aroclor 1242 and total mercury in the Green Bay region sediments and pore waters and to assess the impact of interventions and the natural rates of change previously found.

Atypical Diagenesis and Geochemistry of Redox-Sensitive Elements in Hydrothermal Sediments of the Southern Okinawa Trough

Early diagenesis processes and the geochemistry of redox-sensitive elements (RSEs) in four sediment cores in an active hydrothermal field in the southern Okinawa Trough (OT) was investigated. Dissolved Fe, Mn, ΣHS–, and several other RSEs (Mo, U, and V) in pore water were measured. We also studied metal distribution in sediments using sequential extraction methods. Very high dissolved Fe concentrations (∼140 μmol L–1) but insignificant dissolved Mn were observed in surficial pore waters in the station adjacent to the hydrothermal vent, where highly reactive Fe, Mo, U in the sediments were also measured. Such an atypical diagenetic sequence found in those cores could be driven by the overwhelmingly high reactive Fe fraction (mostly Fe oxides) delivered from the vents. Consequently, significant upward benthic fluxes of Fe and Mo were estimated for the studied stations. In addition, we performed a principal component analysis (PCA), together with relative ratios of carbonate-related elements (Sr, Ca, Mg), to identify particles’ origins in the hydrothermal field; two endmembers being the hydrothermal source and hydrogenous processes. This comprehensive study on a unique set of samples collected by advanced technology provided valuable data to demonstrate distinctive geochemical features that occur in hydrothermal sediments.

Copper-binding ligands in deep-sea pore waters of the Pacific Ocean and potential impacts of polymetallic nodule mining on the copper cycle

The release of potentially toxic metals, such as copper (Cu), into the water column is of concern during polymetallic nodule mining. The bioavailability and thus toxicity of Cu is strongly influenced by its speciation which is dominated by organic ligand (L) complexation in seawater, with L-complexes being considered less bioavailable than free Cu2+. The presence of CuL-complexes in deep-sea sediments has, however, not been systematically studied in the context of deep-sea mining. We thus analyzed the Cu-binding L concentration ([L]) in deep-sea pore waters of two polymetallic nodule provinces in the Pacific Ocean, the Peru Basin and the Clarion-Clipperton-Zone, using competitive ligand equilibration–adsorptive stripping voltammetry. The pore-water dissolved Cu concentration ([dCu]) ranged from 3 to 96 nM, generally exceeding bottom water concentrations (4–44 nM). Based on fitting results from ProMCC and Excel, Cu was predominantly complexed by L (3–313 nM) in bottom waters and undisturbed pore waters. We conclude that processes like deep-sea mining are unlikely to cause a release of toxic Cu2+ concentrations ([Cu2+]) to the seawater as > 99% Cu was organically complexed in pore waters and the [Cu2+] was < 6 pM for 8 of 9 samples. Moreover, the excess of L found especially in shallow pore waters implied that even with a Cu release through mining activities, Cu2+ likely remains beneath toxic thresholds.

Salt composition and biogenic elements in modern pore waters of the Barents Sea (1997–2019)

The data (Cl-, SO42-, Ca2+ Alk and biogenic elements) on the salt composition of pore water and the isotopic organic carbon composition of suspended particulate matter, fluffy layer and surface layers (0–30 cm) of bottom sediments in the Barents and Norwegian seas are discussed during the period of the supposed maximum warming in the Arctic region in the 21st century associated with the “atlantification” of the Arctic Ocean.

A New Dynamic Modeling Approach to Predict Microbial Methane Generation and Consumption in Marine Sediments

Methane, as a clean energy source and a potent greenhouse gas, is produced in marine sediments by microbes via complex biogeochemical processes associated with the mineralization of organic matter. Quantitative modeling of biogeochemical processes is a crucial way to advance the understanding of the global carbon cycle and the past, present, and future of climate change. Here, we present a new approach of dynamic transport-reaction model combined with sediment deposition. Compared to other studies, since the model does not need the methane concentration in the bottom of sediments and predicts that value, it provides us with a robust carbon budget estimation tool in the sediment. We applied the model to the Blake Ridge region (Ocean Drilling Program, Leg 164, site 997). Based on seafloor data as input, our model remarkably reproduces measured values of total organic carbon, dissolved inorganic carbon, sulfate, calcium, and magnesium concentration in pore waters and the in situ methane presented in three phases: dissolved in pore water, trapped in gas hydrate, and as free gas. Kinetically, we examined the coexistence of free gas and hydrate, and demonstrated how it might affect methane gas migration in marine sediment within the gas hydrate stability zone.

Bacteria and Archaea Synergistically Convert Glycine Betaine to Biogenic Methane in the Formosa Cold Seep of the South China Sea

Numerous cold seeps have been found in global continental margins where methane is enriched in pore waters that are forced upward from sediments. Therefore, high concerns have been focused on the methane-producing organisms and the metabolic pathways in these environments because methane is a potent greenhouse gas.

Methane Production and Oxidation in Mangrove Soils Assessed by Stable Isotope Mass Balances

Considerable variability in methane production and emissions has been reported in mangroves, explained by methane inhibition and oxidation. In this study, soil pore waters were collected from mangrove forests located in the Gulf of California (Mexico) exposed to shrimp farm disturbance. The δ13C of dissolved inorganic carbon (DIC) and CH4 were analyzed along with the δ13C of the soil organic matter to assess the proportion of CO2 derived from methanogenesis, its main pathway, and the fraction of methane oxidized. We performed slurry incubation experiments to fit the isotope–mass balance approach. Very low stoichiometric ratios of CH4/CO2 were measured in pore waters, but isotope mass balances revealed that 30–70% of the total CO2 measured was produced by methanogenesis. Mangrove soils receiving effluent discharges shifted the main methanogenesis pathway to CO2 reduction because of an increase in refractory organic matter. Isotope–mass balances of incubations indicated that methane was mainly oxidized by anaerobic oxidation of methane (AOM) coupled to sulfate reduction, and the increase in recalcitrant organic matter should fuel AOM as humus serves as a terminal electron acceptor. Since methanogenesis in mangrove soils is strongly controlled by the oxygen supply provided by mangrove roots, conservation of the forest plays a crucial role in mitigating greenhouse gas emissions.

Ex situ phytoremediation trial of Sardinian mine waste using a pioneer plant species

The mitigation of metals contamination is currently a crucial issue for the reclamation of mine sites. Indeed, mine wastes are often disposed in open dumps and consequently pollutants are subjected to dispersion in the surrounding areas. In this study, the potential use of Helichrysum microphyllum subsp. tyrrhenicum for phytostabilization was evaluated in ex situ conditions. Ninety specimens were randomly selected and were planted in three substrates (reference substrate, mine waste materials, and mine wastes with compost). Mineralogical compositions of substrates, rhizosphere, and roots were assessed through X-ray diffraction (XRD). Zn, Pb, and Cd concentrations of substrates, rhizosphere, soil pore waters, and plant tissues were determined. The phytostabilization potential was determined through the application of biological accumulation coefficient (BAC), biological concentration factor (BCF), and translocation factor (TF). Moreover, survival and biometric parameters were assessed on plant specimens. The polluted substrates and related rhizosphere materials were mainly composed of dolomite, quartz, pyrite, and phyllosilicate. Zn was the most abundant metal in substrates, rhizosphere, and soil pore waters. XRD analysis on roots showed the presence of amorphous cellulose and quartz and Zn was the most abundant metal in plant tissues. H. microphyllum subsp. tyrrhenicum restricts the accumulation of the metals into roots limiting their translocation in aereal parts, indicating its potential use as phytostabilizer (BCF, BAC, TF < 1). Survival and growth data showed a great adaptability to different substrates, with an evident positive effect of the implementation of compost which increased the plant survival and decreased the metals uptake into roots.