Water Chemistry Research Articles

Hydrochemical Characteristics and Evolution under the Influence of Multiple Anthropogenic Activities in Karst Aquifers, Northern China

The intensification of anthropogenic activities (agriculture, industry, and exploitation of water resources) during urbanization has posed significant challenges to the aquatic environment, particularly in karst regions. Karst aquifers are highly susceptible to surface contaminants and exhibit minimal natural remediation capabilities. Our understanding of the anthropogenic activities involved in these sensitive karst systems remains limited. To address this gap, we conducted a comprehensive study, collecting 285 groundwater samples in Feicheng, northern China, from 1996 to 2015. The overexploitation of karst groundwater has resulted in several concerns. The whole dataset was classified into four groups according to land use. Water quality assessments revealed a yearly decline, particularly in industrial and agricultural areas. The water chemistry transitioned from Ca-Mg-HCO3 to Ca-Mg-HCO3-SO4. Such evolution was attributed to natural hydrogeochemical processes, atmospheric precipitation, and anthropogenic inputs. Natural factors included water-rock interactions (the mineral dissolution) and ion exchange. Absolute principal component scores with multiple linear regression (APCS-MLR) were used to quantitatively estimate the sources of pollution. The results showed that hydrogeological settings (recharge, runoff, and discharge) were crucial in the hydrochemistry evolution of karst groundwater systems. In agricultural areas, it is recognized that much of the NO3− accumulation in aquifers came from upstream inputs in the groundwater system, not just irrigation and fertilization. Urban areas were affected by Cl− pollution, primarily due to domestic waste. Industrial regions of recharge zones were more susceptible to atmospheric precipitation and industrial waste, with pollutants infiltrating through rainfall and degrading water quality. Mining areas exhibit higher SO42− and lower pH due to the oxidation of sulfur-containing minerals. Therefore, the rapid response and low self-purification capacity of groundwater in karst regions necessitate caution in urban planning to mitigate impacts on these fragile systems.

Ecological “Windows of opportunity” influence biofilm prokaryotic diversity differently in glacial and non-glacial Alpine streams

In glacier-fed streams, the Windows of Opportunity (WOs) are periods of mild environmental conditions supporting the seasonal development of benthic microorganisms. WOs have been defined based on changes in biofilm biomass, but the responses of microbial diversity to WOs in Alpine streams have been overlooked. A two year (2017–2018) metabarcoding of epilithic and epipsammic biofilm prokaryotes was conducted in Alpine streams fed by glaciers (kryal), rock glaciers (rock glacial), or groundwater/precipitation (krenal) in two catchments of the Central-Eastern European Alps (Italy), aiming at testing the hypothesis that: 1) environmental WOs enhance not only the biomass but also the α-diversity of the prokaryotic biofilm in all stream types, 2) diversity and phenology of prokaryotic biofilm are mainly influenced by the physical habitat in glacial streams, and by water chemistry in the other two stream types. The study confirmed kryal and krenal streams as endmembers of epilithic and sediment prokaryotic α- and β-diversity, with rock glacial streams sharing a large proportion of taxa with the two other stream types. Alpha-diversity appeared to respond to ecological WOs, but, contrary to expectations, seasonality was less pronounced in the turbid kryal than in the clear streams. This was attributed to the small size of the glaciers feeding the studied kryal streams, whose discharge dynamics were those typical of the late phase of deglaciation. Prokaryotic α-diversity of non-glacial streams tended to be higher in early summer than in early autumn. Our findings, while confirming that high altitude streams are heavily threatened by climate change, underscore the still neglected role of rock glacier runoffs as climate refugia for the most stenothermic benthic aquatic microorganism. This advocates the need to define and test strategies for protecting these ecosystems for preserving, restoring, and connecting cold Alpine aquatic biodiversity in the context of the progressing global warming.

Spatial variability in water strontium isotopes and trace metals from the Clarence River Basin, New South Wales, Australia

Understanding fish movement in river systems is essential in identifying habitats which are important for species to perpetuate. Water chemistry, paired with fish otoliths, can be used to trace movements among different habitats, although a detailed understanding of spatial variation in water chemistry is first required. To obtain this knowledge, we analysed surface water collected from 59 sites throughout the Clarence River Basin, a coastal river basin in northern New South Wales, Australia. The primary objective was to quantify the spatial variation of trace metals and strontium isotope ratios (87Sr:86Sr) for future and paired use with otolith microchemistry to track fish movement. Using ICP-OES, we identified that some trace metals, particularly strontium and barium as well as 87Sr:86Sr ratios, varied spatially when analysing all water samples and revealed three distinct regions centring around the estuary, interior and outer regions. These differences were driven by variation in the underlying surface geology between the Clarence–Moreton Basin and the New England Block. Tidal influence also affected trace metals and 87Sr:86Sr ratios throughout the estuarine area. We suggest that the level of differentiation identified in the current study has the potential to discriminate broad-scale fish movements among regions/habitats using otolith analysis, with fine scale movements best elucidated using complementary techniques.

Water residence time is an important predictor of dissolved organic matter composition and drinking water treatability

Freshwater ecosystems are critical resources for drinking water. In recent decades, dissolved organic matter (DOM) inputs into aquatic systems have increased significantly, particularly in central and northern Europe, due to climatic and anthropogenic drivers. The associated increase in dissolved organic carbon (DOC) concentration can change lake ecosystem services and adversely affect drinking water treatment processes. In this study, we examined spatial and temporal patterns of DOM treatability with granular activated carbon (GAC) and biological reactivity based on 14-day bacterial respiration incubations at 11 sites across Mälaren during six-time points between July 2019 and February 2021. Mälaren is the third largest lake in Sweden and provides drinking water for over 2 million people including the capital city Stockholm. In our spatio-temporal analysis, we assessed the influence of phytoplankton abundance, water chemistry, runoff, and climate on DOM composition, GAC removal efficiency, and biological reactivity. Variations in DOM composition were characterized using optical measurements and Orbitrap mass spectrometry. Multivariate statistical analyses indicated that DOM produced during warmer months was easier to remove by GAC. Removal efficiency of GAC varied from 41 to 87 %, and the best predictor of treatability using mass spectrometry was double bond equivalents (DBE), while the best optical predictors were specific UV absorbance (SUVA), and freshness index. The oxygen consumption rate (k) from the bacterial respiration incubations ranged from 0.04 to 0.71 d−1 and higher in warmer months and at deeper basins and was associated with more aliphatic and fresh DOM. The three deepest lake basins with the longest water residence time (WRT) were temporally the most stable in terms of DOM composition and had the highest DOC removal efficiency and k rates. DOM composition in these three lake basins was optically clearer than in basins located closer to terrestrial inputs and had a signature suggesting it was derived from in-lake processes including phytoplankton production and bacterial processing of terrestrial DOM. This means that with increasing WRT, DOM derived from terrestrial sources shifts to more aquatically produced DOM and becomes easier to remove with GAC. These findings indicate WRT can be highly relevant in shaping DOM composition and thereby likely to affect its ease of treatability for drinking water purposes.

The chemical state of the watershed in Ras Elma region (South of Taza, Morocco) one of the parameters responsible for the decline in the formation of the current travertine formations.

The Ras Elma region, situated to the south of the city of Taza in northern Morocco, boasts abundant travertine formations that continue to develop, albeit selectively in specific sheltered sites. This development is influenced by various parameters, including the role of water chemistry. This article presents a spatio-temporal analysis of various hydrochemical parameters, including conductivity, pH, temperature, magnesium, calcium, and others. It's worth noting that the water from the Ras Elma Vauclusian spring, a key driver of travertinization in the region, is sourced from water infiltrating through faults and flowing into Lake Tompraire, known as Dayat Chikker near the Bab Boudir area. The findings suggest that the water in Ras Elma has turned aggressive, as revealed by the examination of the calcaro-carbonic equilibrium. CaCO3 precipitation occurs predominantly in the summer, significantly impacting the formation of travertines, particularly those of the spring and dam types. However, valley-type travertines exhibit more extensive development compared to the other two types.

Reflection of Daily, Seasonal and Interannual Variations in Run-Off of a Small River in the Water Isotopic Composition (δ2H, δ18O): A Case of the Ala-Archa Mountain River Basin with Glaciation (Kyrgyzstan, Central Asia)

Small intermountain river basins are most suitable for developing new methods to estimate water balance due to their well-defined catchment boundaries, relatively rapid runoff processes, and accessible landscapes for study. In general terms, dissecting the hydrograph of a small mountain river requires calibration of the flow model against multi-year data sets, including (a) glacier mass balance and snow water content, (b) radiation balance calculation, (c) estimation of the groundwater contribution, and (d) water discharge measurements. The minimum primary data set is limited to the precipitation and temperature distributions at the catchment. This approach postulates that the conditions for the formation of all components of river flow are known in advance. It is reduced to calculating the dynamic balance between precipitation (input part) and runoff, ablation, and evaporation (output part). In practice, accurately accounting for the inflow and outflow components of the balance, as well as the impact of regulating reservoirs, can be a challenging task that requires significant effort and expense, even for the extensively researched catchments. Our studies indicate the potential benefits of an approach based on one-time, but detailed, observations of stable isotope composition, temperature, and water chemistry, in addition to standard datasets. This paper presents the results of the 2022–2023 work conducted in the basin of the small mountain river Ala-Archa, located on the northern slope of the Kyrgyz Range in Tien-Shan, which was chosen as an example due to its well-studied nature. Our approach could identify previously unknown factors of flow formation and assess the time and effectiveness of work in similar conditions.

Perfluoroalkyl acid adsorption by styrenic β-cyclodextrin polymers, anion-exchange resins, and activated carbon is inhibited by matrix constituents in different ways

Perfluoroalkyl acids (PFAAs) are ubiquitous environmental contaminants of global concern, and adsorption processes are the most widely used technologies to remove PFAAs from water. However, there remains little data on the ways that specific water matrix constituents inhibit the adsorption of PFAAs on different adsorbents. In this study, we evaluated the adsorption of 13 PFAAs on two styrene-functionalized β-cyclodextrin (StyDex) polymers, an activated carbon (AC), and an anion-exchange resin (AER) in the absence and presence of specific water matrix constituents (16 unique water matrices) in batch experiments. All four adsorbents exhibited some extent of adsorption inhibition in the presence of inorganic ions and/or humic acid (HA) added as a surrogate for natural organic matter. Two PFAAs (C5-C6 perfluorocarboxylic acids (PFCAs)) were found to exhibit relatively weak adsorption and five PFAAs (C6-C8 perfluorosulfonic acids (PFSAs) and C9-C10 PFCAs) were found to exhibit relatively strong adsorption on all four adsorbents across all matrices. Adsorption inhibition was the greatest in the presence of Ca2+ (direct site competition) and HA (direct site competition and pore blockage) for AC, NO3- (direct site competition) and Ca2+ (chemical complexation) for the AER, and SO42- (compression of the double layer) for the StyDex polymers. The pattern of adsorption inhibition of both StyDex polymers were similar to each other but different from AC and AER, which demonstrates the distinctive PFAA adsorption mechanism on StyDex polymers. The unique performance of each type of adsorbent confirms unique adsorption mechanisms that result in unique patterns of adsorption inhibition in the presence of matrix constituents. These insights could be used to develop models to predict the performance of these adsorbents in real water matrices and afford rational selection of adsorbents based on water chemistry for specific applications.

A case study on topsoil removal and rewetting for paludiculture: effect on biogeochemistry and greenhouse gas emissions from Typha latifolia, Typha angustifolia, and Azolla filiculoides

Abstract. Rewetting drained peatlands for paludiculture purposes is a way to reduce peat oxidation (and thus CO2 emissions) while at the same time it could generate an income for landowners, who need to convert their traditional farming into wetland farming. The side effect of rewetting drained peatlands is that it potentially induces high methane (CH4) emissions. Topsoil removal could reduce this emission due to the removal of easily degradable carbon and nutrients. Another way to limit CH4 emissions is the choice in paludiculture species. In this study we conducted a field experiment in the coastal area of the Netherlands, in which a former non-intensively used drained peat grassland is rewetted to complete inundation (water table ∼ +18 cm) after a topsoil removal of ∼ 20 cm. Two emergent macrophytes with high potential of internal gas transport (Typha latifolia and Typha angustifolia), and a free floating macrophyte (Azolla filiculoides), were introduced and intensive measurement campaigns were conducted to capture CO2 and CH4 fluxes as well as soil and surface water chemistry. Greenhouse gas fluxes were compared with a high-productive peat meadow as a reference site. Topsoil removal reduced the amount of phosphorus and iron in the soil to a large extent. The total amount of soil carbon per volume stayed more or less the same. The salinity of the soil was in general high, defining the system as brackish. Despite the topsoil removal and salinity, we found very high CH4 emissions for T. latifolia (84.8 g CH4 m−2 yr−1) compared with the much lower emissions from T. angustifolia (36.9 g CH4 m−2 yr−1) and Azolla (22.3 g CH4 m−2 yr−1). The high emissions can be partly explained by the large input of dissolved organic carbon into the system, but it could also be caused by plant stress factors like salinity level and herbivory. For the total CO2 flux (including C-export), the rewetting was effective, with a minor uptake of CO2 for Azolla (−0.13 kg CO2 m−2 yr−1) and a larger uptake for the Typha species (−1.14 and −1.26 kg CO2 m−2 yr−1 for T. angustifolia and T. latifolia, respectively) compared with the emission of 2.06 kg CO2 m−2 yr−1 for the reference site. T. angustifolia and Azolla, followed by T. latifolia, seem to have the highest potential for reducing greenhouse gas emissions after rewetting to flooded conditions (−1.4, 2.9, and 10.5 t CO2 eq. ha−1 yr−1, respectively) compared with reference drained peatlands (20.6 t CO2 eq. ha−1 yr−1). When considering the total greenhouse gas balance, other factors, such as biomass use and storage of topsoil after removal, should be considered. Especially the latter factor could cause substantial carbon losses if not kept in anoxic conditions. When calculating the radiative forcing over time for the different paludicrops, which includes the GHG fluxes and the carbon release from the removed topsoil, T. latifolia will start to be beneficial in reducing global warming after 93 years compared with the reference site. For both Azolla and T. angustifolia this will be after 43 years.

Ecological regulation of chemical weathering recorded in rivers

We provide a new generalized framework accounting for the effects of water and nutrient uptake by roots in the weathering zone on broad patterns of solute concentration - discharge relationships in rivers. As plants withdraw water from the subsurface, they decrease the area-normalized fluid drainage rate. This results in a discharge flux to springs and streams which is a function of water use by plants, leading to ecosystem regulation of the characteristic timescales of chemical weathering reactions and fluid flow rate. Our predictive framework quantifies the pore water and river solute chemistry generated from water-rock interactions, regulated by the effects of vegetation on water flow rates. To this we add the capacity for vegetation to enrich, passively admit, or discriminate against a given dissolved solute based on ecophysiological needs, thus further modifying the local concentration of a given chemical species in solution across a weathering profile. This uptake flux is not lost to the atmosphere in the same manner as water is removed from the subsurface via evapotranspiration. Rather, these extracted chemical species become incorporated into the topsoil as litter which may be partially or fully resolubilized, creating an upper boundary condition which depends on the uptake and recycling characteristics of the ecosystem. These processes are united through a new solution to the advection-reaction equation which allows vegetation to regulate broad patterns of stream concentration - discharge relationships. We show that ecosystems are capable of both accelerating and impeding water-rock reaction rates across the weathering profile, ultimately leading to both thermodynamic and ecological controls on the baseflow concentration of rock-derived solutes in rivers.

Can a naturally depauperate Ephemeroptera, Plectoptera and Trichoptera (EPT) fauna track river degradation in south-western Australia?

Freshwater aquatic ecosystems are threatened globally. Biological monitoring is required to deliver rapid and replicable assessment of changes in habitat quality. The Ephemeroptera, Plectoptera, Trichoptera (EPT) index is a globally recognised rapid bioassessment that measures taxa richness of three insect orders whose larvae are considered sensitive to freshwater habitat degradation. South-western Australia contains threatened freshwater ecosystems but has depauperate EPT fauna and high endemism, potentially reducing the capacity of the EPT index to track degradation. This study investigated if EPT species richness, composition or individual species tracked physical or chemical river degradation in three catchments in south-western Australia. We sampled EPT fauna and measured water chemistry, erosion, sedimentation, riparian vegetation cover and instream habitat at 98 sites in the winters of 2007 and 2023. We found 35 EPT taxa across the study area with a median number of species per site of two. EPT species richness had weak positive associations with a composite water quality index and dissolved oxygen and weak negative associations with electrical conductivity and total nitrogen. No association was found between physical and fringing zone degradation measures and EPT species richness. EPT community structure generally did not distinguish between sites with high or low degradation levels. The presence of the mayfly Nyungara bunni tracked salinity, dissolved oxygen and nitrogen levels, but its usefulness as a bioindicator could be limited by its restricted range. This study suggests that the EPT index would need modification or combination with other indices to be a useful rapid bioassessment in south-western Australia.

A Study on One-Time Inspection for Aging Management of Operating Nuclear Power Plants

One-time inspection is used to confirm the effectiveness of nuclear power plant aging management programs such as water chemistry, fuel oil chemistry, and selective leaching program that is designed to prevent or minimize aging degradation during the plant operation. This paper represents one-time inspection experience of selected components and susceptible locations within the scope of water chemistry and fuel oil chemistry aging management programs. Prior to performing one-time inspection, sample sizes of components to be inspected were determined based on combination of materials, environment and aging effect. Examination techniques and relevant operating experience were analysed to obtain technical basis for further implementation of one-time inspection aging management programs. Existing correlation curves between sample size and total population number were reviewed to prepare further inspections for entire operating plants and ensure safety level of components subject to one-time inspection program.

Seasonal variation in metabolic profiles and microbial communities in a subarctic ore processing plant.

The mining industry strives to reduce its water footprint by recycling water in ore processing. This leads to build-up of ions, flotation chemicals and microbial biomass, which may affect the process. The Boliden Kevitsa mine in Northern Finland is exposed to seasonal change and recycles up to 90% of the process water. We studied the variation in size, composition and putative functions of microbial communities in summer and winter in the ore processing plant. The raw water, Cu and Ni thickener overflow waters had statistically significantly higher bacterial numbers in winter compared to summer, and specific summer and winter communities were identified. Metagenomic analysis indicated that Cu and Hg resistance genes, sulphate/thiosulphate, molybdate, iron(III) and zinc ABC transporters, nitrate reduction, denitrification, thiosulphate oxidation and methylotrophy were more common in winter than in summer. Raw water drawn from the nearby river did not affect the microbial communities in the process samples, indicating that the microbial communities and metabolic capacities develop within the process over time in response to the conditions in the processing plant, water chemistry, used chemicals, ore properties and seasonal variation. We propose that the microbial community structures are unique to the Boliden Kevitsa mine and processing plant.

Geochemical and Isotopic Techniques Constraints on the Origin, Evolution, and Residence Time of Low‐enthalpy Geothermal Water in Western Wugongshan, SE China

AbstractGeothermal resources are increasingly gaining attention as a competitive, clean energy source to address the energy crisis and mitigate climate change. The Wugongshan area, situated in the southeast coast geothermal belt of China, is a typical geothermal anomaly and contains abundant medium‐ and low‐temperature geothermal resources. This study employed hydrogeochemical and isotopic techniques to explore the cyclic evolution of geothermal water in the western Wugongshan region, encompassing the recharge origin, water–rock interaction mechanisms, and residence time. The results show that the geothermal water in the western region of Wugongshan is weakly alkaline, with low enthalpy and mineralization levels. The hydrochemistry of geothermal waters is dominated by Na‐HCO3 and Na‐SO4, while the hydrochemistry types of cold springs are all Na‐HCO3. The hydrochemistry types of surface waters and rain waters are Na‐HCO3 or Ca‐HCO3. The δD and δ18O values reveal that the geothermal waters are recharged by atmospheric precipitation at an altitude between 550.0 and 1218.6 m. Molar ratios of major solutes and isotopic compositions of 87Sr/86Sr underscore the significant role of silicate weathering, dissolution, and cation exchange in controlling geothermal water chemistry. Additionally, geothermal waters experienced varying degrees of mixing with cold water during their ascent. The δ13C values suggest that the primary sources of carbon in the geothermal waters were biogenic and organic. The δ34S value suggests that the sulfates in geothermal water originate from sulfide minerals in the surrounding rock. Age dating using 3H and 14C isotopes suggests that geothermal waters have a residence time exceeding 1 kaBP and undergo a long‐distance cycling process.

Sources and Chemical Weathering Implications of Strontium and Hydrochemistry in an Inland Alpine Permafrost Basin

AbstractThe hydrochemical characteristics of river water are influenced by a multitude of factors, reflecting the surrounding geographical environment. The Shaliu River, located in the northeastern Tibetan Plateau (TP), serves as a typical inland alpine permafrost watershed. In this study, we compiled data on dissolved strontium (Sr) concentration, 87Sr/86Sr isotopic, and hydrochemical profiles from the Shaliu River during the ablation period (May–October). Additionally, we gathered information on the Sr concentration and 87Sr/86Sr in the sediment of the river. The pattern of spatial heterogeneity in observed strontium (Sr) compositions can largely be attributed to lithological characteristics encountered at different locations along the river. The chemical components of Sr in the waters are derived from a combination of carbonate and silicate materials, with carbonates contributing between 69% and 81% and silicates contributing 19%–31%. The annual dissolved Sr flux is estimated to be 132 t/a. In addition to the influence of lithology and weathering processes, we propose that freeze‐thaw cycles within the permafrost layer may significantly affect the chemical mass flux in alpine permafrost watersheds because they generate substantial amounts of loose and easily erodible materials. Climate warming may further intensify the weathering processes in these watersheds, potentially leading to an increase in the Sr flux. This study is crucial for developing a comprehensive understanding of the geochemical composition of dissolved solutes in alpine permafrost regions, as well as for identifying the factors that regulate river water chemistry.

Identification of mine water source based on TPE-LightGBM

Mine water inrush is a serious threat to mine safety production. It is very important to identify water inrush source types quickly to prevent and control water damage. In this study, the aqueous chemical components Na+ + K+, Ca2+, Mg2+, Cl−, SO42− and HCO3− of different aquifers in Pingdingshan coalfield were selected as the characteristic values, and the Surface water, Quaternary pore water, Carboniferous limestone karst water, Permian sandstone water, and Cambrian limestone karst water were used as the labels. An intelligent water source discrimination model is proposed by combining data mining, classification models, and reinforcement learning. As outlier data in the samples may interfere with the model recognition ability, the data distribution range was analyzed using box plots, and 20 groups of abnormal samples were excluded. The processed water chemistry data were divided into 80% learning samples and 20% test samples, and the learning samples were fed into a light gradient boosting machine (LightGBM) for training. The tree-structured parson estimator (TPE) obtains the optimal values of the main parameters of LightGBM in a very short time. Substituting the hyperparameters back into the model yields a 13.9% improvement in the accuracy of the model, proving the effectiveness of the TPE algorithm. To further validate the performance of the model, TPE-LightGBM is compared and analyzed with a Random Search-Multi Layer Perceptron Machine (RS-MLP) and Genetic Algorithm-Extreme Gradient Boosting Tree (GA-SVM). The accuracy of TPE-LightGBM, RS-MLP, and GA-SVM is 0.931, 0.759, 0.724 in that order, and the generalization error RMSE is 0.415, 1.05, and 1.313 in that order. The results show that TPE-LightGBM is more advantageous in water source identification and is more resistant to overfitting. By calculating and comparing the information gain of each variable, the contribution of Ca2+ is the highest, so it is necessary to pay attention to the change in Ca2+ concentration. TPE-LightGBM’s high accuracy and generalization ability have a good prospect for the identification of sudden water source types.

Key factors influencing Hg levels and trends in unperturbed oligotrophic temperate and boreal lakes

Mercury (Hg) is a toxic metal that presents a major risk to ecosystems, biota, human health, and remains a priority concern. In temperate and boreal lakes Hg and methylmercury (MMHg) are expected to vary as a function of atmospheric Hg deposition, lake water chemistry, catchment characteristics and climate variables. The aim of this study was to quantify Hg and MMHg in unperturbed oligotrophic lakes and to identify the factors controlling their distribution. We first hypothesized that lake Hg (and MMHg to lesser extent) spatial variations are linked to atmospheric deposition, catchment characteristics, and terrestrial exportation of dissolved organic carbon (DOC). We secondly examined if lake Hg concentrations have followed the decrease in atmospheric Hg emission observed between the mid-1990s to the end-2010s. We found that overall, atmospheric Hg has little impact on lake Hg and MMHg concentrations, which are both primarily influenced by DOC input originating from the forest catchment. The relationship between DOC and Hg differed between the spring and the fall, with a Hg-to-DOC ratio twice as high in spring. This seems related to snowmelt input of Hg (with a relatively reduced input of DOC) or the internal lake build-up of Hg during the ice-covered period. Of the 10 lakes intensively visited over a 20-year period, only 3 showed significant lake Hg decreases despite significant negative trends in atmospheric Hg concentrations, suggesting a lag between atmospheric and surface water temporal trends. Overall, terrestrial catchments retain around 80% of atmospheric Hg implying that large Hg pools have been built up in soils in the last decades. As such, the reduction of atmospheric Hg alone will not necessarily result in Hg decreases in lakes, since the Hg concentrations may be modulated by DOC export trends and catchment characteristics. This stresses the need to improve our understanding of the processes governing Hg transfers from catchments into lakes.

Groundwater solutes influence the adsorption of short-chain perfluoroalkyl acids (PFAA) to colloidal activated carbon and impact performance for in situ groundwater remediation

Subsurface injection of colloidal activated carbon (CAC) is an in situ remediation strategy for perfluoroalkyl acids (PFAA), but the influence of groundwater solutes on longevity is uncertain, particularly for short-chain PFAA. We quantify the impact of inorganic anions, dissolved organic matter (DOM), and stabilizing polymer on PFAA adsorption to a commercial CAC. Surface characterization supported PFAA chain-length dependent adsorption results and mechanisms are provided. Inorganic anions decreased adsorption for short-chain PFAA (<7 perfluorinated carbons) due to competitive effects, while long-chain PFAA (≥ 7 perfluorinated carbons) were less impacted. DOM decreased adsorption of all PFAA in a chain-length dependent manner. High DOM concentrations (10 mg/L, ∼5 mg OC/L) decreased PFOA adsorption by a factor of 2, PFPeA by one order of magnitude, and completely hindered PFBA adsorption. High MW DOM has less impact on short-chain PFAA than low MW DOM, possibly due to differences in the ability to access CAC micropores. Low DOM concentrations (1 mg/L, ∼0.5 mg OC/L) did not impact adsorption. CMC (90 kDa average MW) had negligible impact on PFAA adsorption likely due to minimal CAC surface coverage. Longevity modeling demonstrated that groundwater solutes limit the capacity for PFAA in a CAC barrier, particularly for short-chain PFAA.

The relationship between cellular protein content and selenium accumulation in freshwater microalgae.

Variability in the bioconcentration of selenium (Se) by primary producers at the base of the food web results in uncertainty in predictions of bioaccumulation and ecological risk to higher trophic level organisms. Water chemistry, speciation of Se, and periphyton community composition have all been suggested as factors that contribute to variability in bioconcentration by primary producers; however, the role of physiological composition of periphyton species in influencing the bioconcentration of Se has not been previously evaluated. To determine if a relationship exists between algal protein content and Se accumulation, Parachlorella kessleri, Chlorella vulgaris, and Raphidocelis subcapitata were exposed to Se (as selenate) and analyzed for total protein and tissue Se content in the exponential and stationary growth phases. Protein content and Se accumulation in R. subcapitata in the stationary phase were also measured under two light intensities. No relationship between cellular protein content and Se accumulation was found for algae in the exponential phase; however, a strong relationship was found in the stationary phase among species and for R. subcapitata under differing light intensities. Absolute Se accumulations by P. kessleri, C. vulgaris, and R. subcapitata in the stationary phase were statistically different; however, the concentrations of Se in protein were similar across species. These results suggest that cellular protein content in microalgae influences Se bioconcentration and that algal protein content may improve Se bioaccumulation modeling in food webs. Integr Environ Assess Manag 2024;00:1-10. © 2024 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Effects of dissolved oxygen on the corrosion-related unidentified deposit formed of 304 SS in the flow accelerated zone under the simulated secondary water chemistry

Effects of dissolved oxygen (DO) on the deposition characteristics of corrosion-related unidentified deposit (CRUD) were investigated by using 304 stainless steel micro-orifices. The main results indicate that the change of DO concentration resulted in a change of the composition of the outermost deposition layer. The DO concentration amplifies/diminishes the porosity in CRUD effect by changing the rate of ion transport. Meanwhile, the electrokinetic effect is weakened by the decrease of the thickness of the electric double layer, which is caused by the dissolution of Cr ions increased by increasing the DO concentration. Meanwhile, the chromium ion concentration increases with the dissolved oxygen concentration, which leads to a decrease in the thickness of the electric double layer, weakening the electrodynamic effect. The above results in the thickness and width of CRUD in the flow acceleration zone vary in varying degrees. This suggests that the deposition process of CRUD occurs under the mechanism of mass transfer and electrokinetic mechanism.

Microbial consortium involved in ferromanganese and francolite biomineralization in an anchialine environment (Zinzulùsa Cave, Castro, Italy)

Tidally-influenced subterranean settings represent natural geomicrobiological laboratories, relatively unexplored, that facilitate the investigation of new biomineralization processes. The unusual water chemistry of Zinzulùsa Cave and its oligotrophic and aphotic conditions have allowed the development of a unique ecosystem in which complex bacterial activities induce rare biomineralization processes. A diversified microbial community develops on centimeter-thick crusts that form in the submerged part of the cave. The crusts are formed of Ca-phosphate minerals, mostly carbonate-fluoroapatite (francolite), covered by a black crust, few microns in thickness, composed of ferromanganiferous oxides (hematite and vernadite). Diffuse coccoidal and filamentous bacteria and amorphous organic matter are mixed with the minerals. The micromorphologies and comparative 16S rRNA gene-based metabarcoding analyses identify a “core microbiota” also common to other natural environments characterized by FeMn and Ca-phosphate mineralization. The microbiota is characterized by nitrifying, sulfide/sulfur/thiosulfate-oxidizing and sulfate/thiosulfate/sulfur-reducing bacteria. In addition, manganese-oxidizing bacteria include the recently described “Ca. Manganitrophus noduliformans” and an abundance of bacteria belonging to the Planctomycetes-Verrucomicrobia-Chlamydiae (PVC) superphylum, as well as Haliangiales (fruiting body-forming bacteria) and Hyphomicrobiales (stalked and budding bacteria) that are known to produce extracellular polymers that trap iron and manganese oxides. 16S rRNA gene metabarcoding analysis showed the presence of bacteria able to utilize many organic P substrates, including Ramlibacter, and SEM images revealed traces of fossilized microorganisms resembling “cable bacteria”, which may play a role in Ca-phosphate biomineralization. Overall, the data indicate biomineralization processes induced by microbial metabolic activities for both ferromanganiferous oxide and francolite components of these crusts.