Water Concentration Research Articles

Investigation of occurrence of aromatic amines in municipal wastewaters using passive sampling

Aromatic amines (AAs) are human-made compounds known for their mutagenic properties, entering surface waters from various sources, often originating as transformation products of dyes or pesticides. Despite their low concentrations in surface waters, AAs can exhibit mutagenicity. Our study focused on evaluating three passive samplers (PSs) for enriching these compounds from influent and effluent of a wastewater treatment plant (WWTP) in Brno, Czech Republic. The PSs tested included variants containing AttractSPE™ SDB-RPS sorbent disk, one with and one without a diffusive agarose hydrogel layer, and a modified Speedisk (Bakerbond Speedisk® H2O-Philic). PSs were deployed in wastewater (WW) for one to four weeks in various overlapping combinations, and the uptake of AAs to PSs was compared to their concentrations in 24-hour composite water samples. A targeted LC/MS analysis covered 42 amines, detecting 11 and 13 AAs in daily composite influent and effluent samples, respectively. In the influent, AAs ranged from 1.5 ng L−1 for 1-anilinonaphthalene to 1.0 μg L−1 for aniline, and the highest concentration among all measured amines was observed for cyclohexylamine at 2.9 μg L−1. In the effluent, concentrations ranged from 0.5 ng L−1 for 1-anilinonaphthalene to 88 ng L−1 for o-anisidine. PSs demonstrated comparable accumulation of amines, with integrative uptake up to 28 days in both influent and effluent and detection of up to 23 and 27 amines in influent and effluent, respectively; altogether 34 compounds were detected in the study. Sampling rates (Rs) were estimated for compounds present in at least 50 % of the samples and showing <40 % aqueous concentration variability, with robustness evaluated by comparing values for compounds in WWTP influent and effluent. Although all devices performed similarly, hydrogel-based PS exhibited superior performance in several criteria, including time integration and robustness of sampling rates, making it a suitable monitoring tool for AAs in WW.

Seasonal dynamics and ecological risks of organochlorine pesticides in Kafrelsheikh-Egypt: Implications for aquatic ecosystems and public health

Kafrelsheikh, situated in the middle of the Nile Delta, significantly contributes to Egypt's aquaculture and agriculture sectors. However, the local use of organochlorine pesticides (OCPs) in agriculture is often a source of OCP residues in associated drainage waters, which may threaten aquatic ecosystems. These pesticides persist in local water bodies, jeopardizing aquatic ecosystems and potentially impacting human health. This comprehensive study assessed the seasonal variations of 17 OCPs in both water sources and Nile tilapia across eight fish farming locations in Kafrelsheikh. Using gas chromatography coupled with mass spectrometry (GC-MS), we detected OCP concentrations in water that varied seasonally where winter recorded the highest levels at 22.5 ng/mL and, summer showed the lowest levels at 6.2 ng/mL. Despite water samples occasionally showing risk quotients (RQs) greater than 1, indicating a potential threat to aquatic life, the OCP levels in Nile tilapia were sufficiently low, with target hazard quotients (THQ) below 1, suggesting no significant risk for human consumption. The research highlights a pressing need for regular environmental monitoring and stricter regulatory control over pesticide use to protect aquatic life and ensure the safety of aquaculture products. These findings provide a critical basis for policy-making, aimed at balancing agricultural productivity with environmental sustainability in regions heavily dependent on both.

Methane Combustion Kinetics over Palladium-Based Catalysts: Review and Modelling Guidelines

Fugitive methane emissions account for a significant proportion of greenhouse gas emissions, and their elimination by catalytic combustion is a relatively easy way to reduce global warming. New and novel reactor designs are being considered for this purpose, but their correct and efficient design requires kinetic rate expressions. This paper provides a comprehensive review of the current state of the art regarding kinetic models for precious metal catalysts used for the catalytic combustion of lean methane mixtures. The primary emphasis is on relatively low-temperature operation at atmospheric pressure, conditions that are prevalent in the catalytic destruction of low concentrations of methane in emission streams. In addition to a comprehensive literature search, we illustrate a detailed example of the methodology required to determine an appropriate kinetic model and the constants therein. From the wide body of literature, it is seen that the development of a kinetic model is not necessarily a trivial matter, and it is difficult to generalize. The model, especially the dependence on the water concentration, is a function of not only the active ingredients but also the nature of the support. Kinetic modelling is performed for six catalysts, one commercial and five that were manufactured in our laboratory, for illustration purposes.

Noble gas characteristics of microbial gas in the Qaidam Basin, China: Implications for helium enrichment processes

Helium is a critical, strategic and nonrenewable resource with limited reserves and unstable supplies. However, the helium sources and migration processes in petroliferous basins remain unclear. The Qaidam Basin features multiple reservoir layers, multiple genetic types of natural gas, and varying helium concentrations, providing an ideal natural laboratory for understanding the helium enrichment processes. Here, we present the original noble gas isotopic compositions and major gas components of 11 microbial gas samples from three gas layers in the Sebei No.1 gas field, eastern Qaidam Basin, China. The helium isotopic ratios range from 0.007 to 0.057 Ra, reflecting a predominantly crustal source. The Quaternary Sebei microbial gas features much lower helium concentration (0.0003–0.001%), 21Ne/22Ne ratio (0.031–0.034), and 40Ar/36Ar ratio (292–380) than thermogenic natural gases in the Qaidam Basin. The middle gas layer (II) of the Sebei gas field features higher 21Ne/22Ne and 40Ar/36Ar ratios than the top and bottom gas layers, displaying positive correlations with higher 4He groundwater concentrations before degassing, as calculated from 4He/20Ne ratios and 20Ne concentrations in air-saturated water. However, the correlations between the 4He contents in natural gas and the 21Ne/22Ne and 40Ar/36Ar ratios are unclear, suggesting that 4He dissolves into the groundwater system before degassing into a gas reservoir and that the variations in the 4He concentration in the gas phase are caused by the different levels of hydrocarbon dilution. Quantitative calculations of helium production revealed an external helium flux from the crustal basement except for the in-situ production from sedimentary strata even in this broadly-defined self-generating and self-preserving natural gas system. The helium resources in the Qaidam Basin are mainly distributed in tectonically active zones with uplifted pre-Jurassic basement rocks (providing sufficient helium sources), ancient groundwater systems (accumulating more helium) and suitable hydrocarbon production (acting as a carrier gas but diluting helium as slightly as possible).

Trade-offs between nitrogen and phosphorus removal with floodplain remediation in agricultural streams

To improve water quality and reduce instream erosion, floodplain remediation along agricultural streams can provide multiple ecosystem services through biogeochemical and fluvial processes. During floodplain inundation, longer water residence time and periodic anoxic conditions can lead to increased nitrogen (N) removal through denitrification but also mobilization of phosphorus (P), impeding overall water quality improvements. To investigate the capacity for N and P processing in remediated streams, we measured potential denitrification and nitrous oxide production and yields together with potential P desorption and P fractions in floodplain and stream sediments in ten catchments in Sweden. Sediment P desorption was measured as equilibrium P concentration, using P isotherm incubations. Denitrification rates were measured with the acetylene inhibition method. Sediment nutrient process rates were combined with hydrochemical monitoring along remediated streams and their paired upstream control reaches of trapezoidal shape to determine the impact of floodplains on water quality. The correlation between floodplain denitrification rates and P desorption (r = 0.53, p = 0.02) revealed a trade-off between soluble reactive P (SRP) and nitrate removal, driven by stream water connectivity to floodplains. Nitrous oxide production was not affected by differences in P processing, but nitrous oxide yields decreased with higher denitrification and P desorption. The release of SRP from floodplains (0.03 ± 0.41 mg P kg−1 day−1) was significantly lower than from trapezoidal stream banks (0.38 ± 0.37 mg P kg−1 day−1), predicted by long-term SRP concentrations in stream water and floodplain inundation frequency. The overall impact of SRP release from floodplains on stream SRP concentrations in remediated reaches was limited. However, the remediated reaches showing increased stream SRP concentrations were also frequently inundated and had higher labile P content and coarse soil texture in floodplain sediments. To fully realize the potential for water quality improvements with constructed floodplains in agricultural streams, the promotion of denitrification through increased inundation should be balanced against the risk of P release from sediments, particularly in streams with high SRP inputs.

Severe microplastic pollution risks in urban freshwater system post-landfill fire: A case study from Brahmapuram, India

To investigate the escalating issue of microplastic (MP), pollution in urban water bodies, this study focuses on the aftermath of the Brahmapuram landfill fire in Kochi, India, analyzing its impact on MP concentrations in nearby freshwater system. The study conducted sampling sessions at the landfill site immediately before and after the fire. Post-fire, findings demonstrated a substantial increase in MP concentrations in surface waters, with levels rising from an average 25793.33 to 44863.33 particles/m³, featuring a notable presence of larger, predominantly black MPs. Sediment samples showed no significant change in MP count, but there was a significant increase in mass concentration. SEM/EDS analysis revealed changes in surface morphology and elemental composition, suggesting thermal degradation. Risk assessment using the Microplastic Pollution Index (MPI) and Risk Quotient (RQ) methods indicated heightened MP pollution risk in surface water post-fire. Hierarchical cluster analysis revealed the landfill's proximity as a significant factor influencing MP characteristics in the aquatic system. The study highlights the escalated challenge of MP pollution in urban water bodies following environmental disasters like landfill fires, underscoring the urgent need for policy and environmental management strategies.

Linking Upwelling Dynamics and Subsurface Nutrients to Projected Productivity Changes in the California Current System

AbstractGiven the importance of coastal upwelling systems to ocean productivity, fisheries, and biogeochemical cycles, their response to climate change is of great interest. However, there is no consensus on future productivity changes in these systems, which may be controlled by multiple drivers including wind‐driven and geostrophic transport, stratification, and source water properties. Here we use an ensemble of regional ocean projections and recently developed upwelling indices for the California Current System to disentangle these sometimes‐competing influences. Some changes are consistent among models (e.g., decreased mixed layer depth), while for others there is a lack of agreement even on the direction of future change (e.g., nitrate concentration in upwelled waters). Despite models' diverging projections of productivity changes, they agree that those changes are predominantly driven by subsurface nitrate concentrations, not by upwelling strength. Our results highlight the need for more attention to processes governing subsurface nutrient changes, not just upwelling strength.

A hybrid deep learning approach to predict hourly riverine nitrate concentrations using routine monitored data

With high-frequency data of nitrate (NO3–N) concentrations in waters becoming increasingly important for understanding of watershed system behaviors and ecosystem managements, the accurate and economic acquisition of high-frequency NO3–N concentration data has become a key point. This study attempted to use coupled deep learning neural networks and routine monitored data to predict hourly NO3–N concentrations in a river. The hourly NO3–N concentration at the outlet of the Oyster River watershed in New Hampshire, USA, was predicted through neural networks with a hybrid model architecture coupling the Convolutional Neural Networks and the Long Short-Term Memory model (CNN-LSTM). The routine monitored data (the river depth, water temperature, air temperature, precipitation, specific conductivity, pH and dissolved oxygen concentrations) for model training were collected from a nested high-frequency monitoring network, while the high-frequency NO3–N concentration data obtained at the outlet were not included as inputs. The whole dataset was separated into training, validation, and testing processes according to the ratio of 5:3:2, respectively. The hybrid CNN-LSTM model with different input lengths (1d, 3d, 7d, 15d, 30d) displayed comparable even better performance than other studies with lower frequencies, showing mean values of the Nash-Sutcliffe Efficiency 0.60–0.83. Models with shorter input lengths demonstrated both the higher modeling accuracy and stability. The water level, water temperature and pH values at monitoring sites were main controlling factors for forecasting performances. This study provided a new insight of using deep learning networks with a coupled architecture and routine monitored data for high-frequency riverine NO3–N concentration forecasting and suggestions about strategies about variable and input length selection during preprocessing of input data.

Improving the Properties of Gelatin-Based Films by Incorporation of "Pitanga" Leaf Extract and Crystalline Nanocellulose.

Biopolymer-based films can be activated by the incorporation of active compounds into their matrix. Plant extracts are rich in phenolic compounds, which have antimicrobial and/or antioxidant properties. The aim of this study was to produce gelatin-based active films and nanocomposite films incorporated with "pitanga" (Eugenia uniflora L.) leaf extract (PLE) and/or crystalline nanocellulose extracted from soybean straw (CN), and to study the physicochemical, functional, microstructural, thermal, UV/Vis light barrier, and antioxidant properties of these materials. PLE enhanced some film properties, such as tensile strength (from 30.2 MPa to 40.6 MPa), elastic modulus (from 9.3 MPa to 11.3 MPa), the UV/Vis light barrier, and antioxidant activity, in addition to affecting the microstructural, surface, and color properties. These improvements were even more significant in nanocomposites simultaneously containing PLE and CN (59.5 MPa for tensile strength and 15.1 MPa for elastic modulus), and these composites also had lower moisture content (12.2% compared to 13.5-14.4% for other treatments) and solubility in water (from 48.9% to 44.1%). These improvements may be the result of interactions that occur between PLE's polyphenols and gelatin, mainly in the presence of CN, probably due to the formation of a stable PLE-CN-gelatin complex. These results are relevant for the food packaging sector, as the activated nanocomposite films exhibited enhanced active, barrier, and mechanical properties due to the presence of PLE and CN, in addition to being entirely produced with sustainable components from natural and renewable sources.

Understanding arsenic-ulexite interactions in evaporite environments: Evidence from XRPD, micro-XRF, micro-FT-IR, and XPS studies

World-class borate deposits often form from As-rich waters, this study addresses the understudied association of arsenic (As) species with evaporite borates, focusing on the Puna region's borate deposits (Central Andes of Argentina). The research aims to characterize the association between borate minerals and high As concentrations in brines and thermal waters. To achieve this, five borate samples were collected from the Olaroz salt flat nucleus and thermal springs, alongside associated water samples. Comprehensive analytical techniques, including ICP-MS, ICP-OES, synchrotron-based micro-XRF, XRPD, Rietveld analysis, micro-FT-IR, and XPS, were employed to determine bulk and surface chemical compositions, mineral identification, and solid speciation of As and boron. The study reveals that under oxidizing conditions and in absence of organic matter, aqueous arsenic species interact with ulexite through a stepwise process involving charge neutralization, cationic bridge formation, and surface complex formation with polyborate and As(V) oxyanions. However, in environments associated with microbial mats or organic-rich sediments, the dissolved As(V) is reduced to As(III), which forms complexes with functional groups of organic matter. The coexistence of As(III) and As(V) in specific layers suggests potential remediation strategies targeting organic matter for the removal of the more toxic As(III) in similar geological settings.

Co-occurrence of elevated arsenic and fluoride concentrations in Wuliangsu Lake: Implications for the genesis of poor-quality groundwater in the (paleo-)Huanghe (Yellow River) catchment, China

The co-occurrence of high As and F concentrations in saline groundwater in arid and semi-arid regions has attracted considerable attention. However, the factors determining the elevated concentrations of the two elements in surface water in these regions have not been sufficiently studied, and their implications for the poor-quality of local groundwater (high levels of As, F, and salinity) are unknown. A total of 18 water samples were collected from Wuliangsu Lake, irrigation/drainage channels, and the Huanghe (i.e., Yellow River) in the Hetao Basin, China. The pH, concentrations of As and F as well as those of other major elements, and stable isotope (H and O) compositions were analyzed. The water samples had a high pH (7.85–9.01, mean 8.25) and high TDS (402–9778 mg/L, mean 1920 mg/L) values. In six of the 10 lake samples, As concentration was above 10 μg/L (maximum 69.1 μg/L) and, in one of them, F concentration was above 1.5 mg/L. Interestingly, the high As, F, and TDS values simultaneously detected in the lake water were similar to those previously reported in local groundwater, and all water samples showed a significant positive correlation between As and F concentrations (R2 = 0.96, p < 0.01), except for two samples with abnormally high Ca2+ levels. The results of stable isotope analysis and Cl/Br ratios suggested that the lake experienced strong evaporation, which is consistent with the high TDS values. Evaporative concentration is suggested as the main factor contributing to the elevated As and F concentrations in the lake water. In addition, the major ions (e.g., Na+, Cl−, HCO3−, and OH−) and pH in the lake water increased during evaporation, leading to desorption of As and F. Thus, the evaporation process, including evaporative concentration and desorption, was considered primarily responsible for the elevated As and F in the lake water. Based on the results of this study, we presume that the paleolakes in the study area have experienced intense evaporation process. As a result, As, F, and major elements accumulated in sediments (or residual lake water) and were buried in the fluvial basins; then, they were released into the groundwater through multiple (bio)hydrogeochemical processes. By combining the results of this study with those obtained from previous groundwater analyses, we propose a new hypothesis explaining the origin of elevated As and F concentrations in saline groundwater in arid and semi-arid regions.

Assessment and accumulation of microplastics in the Indian riverine systems: Risk assessment and implications of translocation across the water-to-fish continuum

Microplastic (MP) pollution has engulfed global aquatic systems, and the concerns about microplastic translocation and bioaccumulation in fish and other aquatic organisms are now an unpleasant truth. In the past few years, MP pollution in freshwater systems, particularly rivers and subsequently in freshwater organisms, especially in fish, has caught the attention of researchers. Rivers provide livelihood to approximately 40 % of the global population through food and potable water. Hence, assessment of emerging contaminants like microplastics in rivers and the associated fauna is crucial. This study assessed microplastics (MPs) in fish, sediment and freshwater samples across the third largest riverine system of peninsular India, the Mahanadi River. The number concentrations of MPs measured in water, sediment and fish ranged from 337.5 ± 54.4–1333.3 ± 557.2 MPs/m3, 14.7 ± 3.7–69.3 ± 10.1 MPs/kg. Dry weight and 0.4–3.2 MPs/Fish, respectively. Surprisingly, MPs were found in every second fish sample, with a higher MP number in the gut than in the gills. Black and blue coloured filaments with <0.5 mm size were the dominant MPs with polypropylene and polyethylene polymers in abundance. The Polymer Hazard Index (PHI) and the Potential Ecological Risk Index (PERI) studies revealed that the majority of the sampling sites fell in Risk category V (dangerous category). An irregular trend in the MP concentration was observed downstream of the river, though relatively elevated MP concentrations in water and fish samples were observed downstream of the river. t-Distributed Stochastic Neighbour Embedding (t-SNE) unveiled distinct patterns in MP distribution with a higher similarity exhibited in the MPs found in fish gill and gut samples, unlike water and sediment, which shared certain characteristics. The findings in the current study contribute to filling the knowledge gap of MP assessment and accumulation in global freshwater systems and highlight the microplastic contamination and accumulation in fish with its potential implications on human health.

AgriTera: Accurate Non-Invasive Fruit Ripeness Sensing via Sub-Terahertz Wireless Signals

The potential to transform the agriculture sector and reduce food waste significantly lies in the ability to assess the quality of fruits and vegetables on a large scale. This article introduces AgriTera, an innovative solution that utilizes sub-terahertz wireless signals for accurate and non-invasive fruit ripeness sensing, without the need for physical contact. The underlying idea is that sugar and water concentrations in fruits, linked to ripening, create distinctive patterns in the wideband spectrum of reflected signals from the fruit body. AgriTera leverages the sub-THz bands due to their wide bandwidth, sensitivity to water, millimeter-scale penetration depth, and non-ionizing features. This enables high-resolution inferences from both the peel and pulp underneath. A chemometric model is developed to translate reflection spectra into well-known ripeness metrics like Dry Matter and Brix. Extensive over-the-air experiments using commercial sub-THz transceivers are conducted and compared with ground truth values from specialized sensors and a vision-based scheme.

CH4 emissions from runoff water of Alaskan mountain glaciers

Recent studies have observed high methane concentrations in runoff water and the ambient air at various glacier sites, including the Greenland Ice Sheet, the glacier forefield in Svalbard, and the ice cap in Iceland. This study extends these findings to smaller mountain glaciers in Alaska. Methane and carbon dioxide concentrations in the ambient air near the meltwater outlet, fluxes of these gases at the surface of runoff water and riverbank sediments, and dissolved methane content in the runoff water were measured at four glaciers. Three of the four glaciers showed conspicuous signals of methane emissions from runoff water, with the Castner Glacier terminus exhibiting a methane concentration three times higher than background levels, along with elevated dissolved methane levels in the runoff water. This study marks the detection of significant methane emissions from small mountain glacier runoff, contributing to the understanding that mountain glaciers also release methane into the atmosphere.

A method for studying the influence of Mn oxyhydroxides on the trace element content of aquatic bryophytes

The main objective of this study was to develop and test a method of separating externally deposited Mn oxyhydroxides and co-precipitated elements from samples of aquatic moss (the moss Fontinalis antipyretica). The method, which uses 0.1 M hydroxylamine to dissolve the oxyhydroxides, was tested with samples collected in rivers with slightly acidic, well‑oxygenated waters, where high rates of Mn precipitation occur. The method was effective (it extracted up to 84 % of the Mn) and selective (Fe oxyhydroxides were not extracted). The elements Ba, Cd, Zn and Ni were associated with the Mn oxyhydroxides, while Al, As, Cr, Cu, Fe, Hg and Pb were not. Deposition of Mn therefore increased the concentration of some elements in the moss samples. However, as Mn precipitation depends on Eh and pH, which are independent of the concentrations of the elements in water, the relationship between water and moss element concentrations is not clear (i.e. the data are noisy). This is a problem in biomonitoring studies, which assume a close relationship between element concentrations in moss and water. The value of the proposed extraction method is that it can be used to correct the effect of Mn deposition. We present an example of this correction applied to the Cd concentrations in the test data. We found that the noise introduced by the Mn, including age-related effects (observed by comparing concentrations in 0–2.5 and 2.2–5.0 cm sections from the shoot apex), can be reduced. Additionally, the correction revealed recent increases in Cd concentrations in one site that were not observed in the uncorrected data. Another finding of interest was the low content of total Mn and different extractability (of most elements) observed in moss samples collected in alkaline waters. Finally, we discuss how future studies designed for different environmental scenarios can benefit from application of the proposed method.

Modeling and FE simulation of coupled water diffusion and viscoelasticity in relaxation tests of polyamide 6

AbstractPolyamides can absorb or desorb water from or to their surrounding environment. The impact of this process is significant as water molecules lead locally to a swelling and a coupling of diffusion and deformation behavior. To model these phenomena, a strongly coupled chemo-mechanical (or diffuso-mechanical) model is required, considering both local water concentration and the viscoelastic material behavior of polyamide. In the present work, we derive and apply such a model to polyamide 6. A diffusion equation describing changes in water concentration is coupled to the balance of linear momentum in polyamide 6. The interaction between deformation and concentration is derived from thermodynamic considerations by introducing a free energy consisting of a mechanical and a chemical part. The mechanical part describes a linear viscoelastic model and includes chemical strains due to the presence of water molecules. The chemical part builds upon the theory of Flory and Huggins, that takes into account changes in enthalpy and entropy of mixing due to the interaction of polymer and water molecules. The coupling of deformation to water concentration arises due to a dependency of the water flux on the hydrostatic stress inside the polyamide. We successfully apply the derived model in Finite-Element simulations to predict the drying of polyamide 6 specimens without any coupling to mechanical loads. In addition, we reproduce experimentally obtained data from relaxation measurements, where the drying of polyamide specimens leads to an increase in relaxation modulus.

Conformations of a highly expressed Z19 α-zein studied with AlphaFold2 and MD simulations.

α-zeins are amphiphilic maize seed storage proteins with material properties suitable for a multitude of applications e.g., in renewable plastics, foods, therapeutics and additive manufacturing (3D-printing). To exploit their full potential, molecular-level insights are essential. The difficulties in experimental atomic-resolution characterization of α-zeins have resulted in a diversity of published molecular models. However, deep-learning α-zein models are largely unexplored. Therefore, this work studies an AlphaFold2 (AF2) model of a highly expressed α-zein using molecular dynamics (MD) simulations. The sequence of the α-zein cZ19C2 gave a loosely packed AF2 model with 7 α-helical segments connected by turns/loops. Compact tertiary structure was limited to a C-terminal bundle of three α-helices, each showing notable agreement with a published consensus sequence. Aiming to chart possible α-zein conformations in practically relevant solvents, rather than the native solid-state, the AF2 model was subjected to MD simulations in water/ethanol mixtures with varying ethanol concentrations. Despite giving structurally diverse endpoints, the simulations showed several patterns: In water and low ethanol concentrations, the model rapidly formed compact globular structures, largely preserving the C-terminal bundle. At ≥ 50 mol% ethanol, extended conformations prevailed, consistent with previous SAXS studies. Tertiary structure was partially stabilized in water and low ethanol concentrations, but was disrupted in ≥ 50 mol% ethanol. Aggregated results indicated minor increases in helicity with ethanol concentration. β-sheet content was consistently low (∼1%) across all conditions. Beyond structural dynamics, the rapid formation of branched α-zein aggregates in aqueous environments was highlighted. Furthermore, aqueous simulations revealed favorable interactions between the protein and the crosslinking agent glycidyl methacrylate (GMA). The proximity of GMA epoxide carbons and side chain hydroxyl oxygens simultaneously suggested accessible reactive sites in compact α-zein conformations and pre-reaction geometries for methacrylation. The findings may assist in expanding the applications of these technologically significant proteins, e.g., by guiding chemical modifications.

Drivers of neritic water intrusions at the subtropical front along a narrow shelf

The near-ubiquitous presence of freshwater over the inner to mid-continental shelf off of the Otago Peninsula in southeast Aotearoa/New Zealand has been previously identified in long-term cross-shelf transects. Occasional influxes of this silicate-rich neritic water past the shelf break and beyond the Subtropical Front have been observed, potentially supporting elevated chlorophyll-a concentrations in SubAntarctic waters. Nearshore salinity variability has been connected to flow rates of the Clutha River, Aotearoa’s largest river by discharge, however, other physical mechanisms influencing the structure of freshwater along this coast have not been explicitly explored. A numerical model of Aotearoa’s southeast continental shelf forced with realistic discharge from the Clutha River is used to assess the drivers of river plume variability and identify conditions associated with the transport of neritic water beyond the shelf break. Event scale, lagged correlation, EOF, and composite analysis of a model passive dye tracer revealed three generalised plume structures that are dependent on river discharge, along-front wind stress, and shelf current velocities. Downfront wind stress suppresses bulge formation at the river mouth and constrains the river plume against the coast, whereas upfront wind stress causes the river plume to move offshore over the shelf and spread across the upper water column. Rarely, upfront wind stress generates a nearshore current reversal over the shelf, causing the plume to deflect straight off-shelf and across the shelf edge before meeting the frontal current and advecting to the northeast. Future observational work is required to validate the mechanisms described and address the biological implications of these findings.

Sources, Fates, and Geochemical Cycling of Mercury in Geothermal Fields: Insights From Mercury Isotopes

AbstractGeothermal fields emit remarkable amounts of mercury (Hg) to the environment. To address the source, fate and geochemical cycling of Hg in geothermal fields, we investigated Hg concentrations and isotopic compositions of hot spring water and fumarole gases from Rehai and Dagejia in SW‐China. Elevated Hg concentrations in fumarole gases (10.0–167 ng m−3) and hot spring water (3.44–84.5 ng L−1) were observed, suggesting that both geothermal fields are of environmental concern. The variation in Δ199Hg (−0.06 to 0.23‰) and Δ200Hg (−0.09 to 0.19‰) in hot spring water supports Hg likely originating from endogenous volcanic degassing and/or rainwater. Negative and nearly zero Δ199Hg in fumarole gases (−0.32 to 0.03‰) supports volcanic degassing and background atmosphere origin. The ranges of δ202Hg in fumarole gases (−0.74 to 0.59‰) and hot spring water (−1.29 to 0.52‰) could reflect limited fluids boiling in geothermal fields. This study, thus, fills an important knowledge gap regarding Hg global cycling.

Selective metasomatism of ultramafic cumulates within Archean supracrustal sequences

The Neoarchean Storø Supracrustal Belt in SW Greenland comprises a sequence of mature quartzite, metapelite, amphibolite, and ultramafic rocks that underwent amphibolite facies metamorphism during the amalgamation of the Mesoarchean Akia Terrane and the Eoarchean Færingehavn Terrane. In this belt, tourmaline is found in a transition zone between ultramafic and metapelitic rocks, but also occurs as orbicules within the ultramafic rocks. These tourmaline orbicules hosted by ultramafic rocks are reported for the first time in the North Atlantic craton, thus indicating a unique formation mechanism. We conducted a comprehensive examination of the petrology, whole-rock and mineral chemistry, and oxygen isotope compositions from borehole samples in the Storø Supracrustal Belt, to elucidate the metasomatic events associated with the formation of the orbicular tourmalines. The Storø ultramafic rocks have high MgO, Cr, and Ni contents, with low abundances of REE and HFSE, and preserve a typical cumulate texture. These features are similar to those of ultramafic cumulates found in other Archean supracrustal belts, suggesting a cumulate origin for the Storø ultramafic rocks. Furthermore, the morphology and composition of the tourmaline orbicules within these cumulates indicate that they originated from melts with high boron and high water concentrations that infiltrated the ultramafic rocks. The main factor influencing the morphology of the tourmaline orbicules is the silicification of the ultramafic rocks, driven by their lower chemical potential of SiO2 compared to the surrounding rocks. This silicification process, in combination with compositional variations of cumulates during fractional crystallization, has contributed to the geochemical diversity observed in Archean ultramafic rocks. Thus, it is crucial to understand the effects of such selective metasomatism on Archean ultramafic rocks, as this will facilitate the extraction of original information preserved in the early rock record.