Changes In Water Chemistry Research Articles

Macrophyte coverage drives microbial community structure and interactions in a shallow sub-tropical lake

Shallow lakes are typically dominated by macrophytes, which have important functional roles regulating trophic conditions and creating biological habitat. Macrophytes have been shown to strongly influence water chemistry and shape microbial communities in shallow lakes. In Florida, many large, shallow lakes are dominated by alien invasive, submersed macrophytes, such as hydrilla (Hydrilla verticillata [L.F.] Royle) and are intensively managed to reduce infestations and contain the spread of these alien invasive macrophytes. In this study, we investigated the effects of large (40 ha) herbicidal and mechanical control treatments on a large lake located in Central Florida that resulted in the reduction of Hydrilla and concomitant changes in water chemistry and microbial communities (both bacteria and protists [microbial eukaryotes]). We observed a considerable decrease in macrophyte coverage associated with plant control treatments as well as a temporal change in macrophyte coverage in Lake Tohopekaliga. We found that changes in macrophyte coverage, regardless of treatment type, significantly affected the water chemistry of the lake, resulting in a sharp increase of chlorophyll a concentration as well as an increase in turbidity with the decrease of macrophyte coverage. Moreover, the decline in macrophytes led to decreases in microbial community diversity with over-representation of phototrophic functional groups. Specifically, we observed an increase in cyanobacteria with the decrease in macrophyte coverage. Our study highlights the advantages and disadvantages of macrophyte control. Although there was an initial decrease in macrophyte coverage associated with the chemical and mechanical control of aquatic plants, after a few months, we found a considerable increase in coverage. In addition, the increase of cyanobacterial relative abundance demonstrates the possible consequences of aquatic plant control such as cyanobacterial blooms if there is a continued decline of macrophytes.

Anthropogenic bottom-up and top-down impacts on boreal breeding waterbirds.

Wetland habitats are changing under multiple anthropogenic pressures. Nutrient leakage and pollution modify physico-chemical state of wetlands and affect the ecosystem through bottom-up processes, while alien predators affect the ecosystems in a top-down manner. Boreal wetlands are important breeding areas for several waterbird species, the abundances of which potentially reflect both bottom-up and top-down ecosystem processes. Here, we use long-term national monitoring data gathered from c. 130 waterbird breeding sites in Finland from the 1980s to the 2020s. We hypothesised that the physico-chemical state of the waters and increasing alien predator abundance both play a role in steering the waterbird population trends. We set out to test this hypothesis by relating population changes of 17 waterbird species to changes in water chemistry and to regional alien predator indices while allowing species-specific effects to vary with foraging niche (dabblers, invertivore divers, piscivorous divers, herbivores), nesting site, female mass and habitat (oligotrophic, eutrophic). We found niche and nesting site-specific, habitat-dependent changes in waterbird numbers. While the associations with higher phosphorus levels and browning water were in overall positive at the oligotrophic lakes, the numbers of invertivore and piscivore diving ducks were most strongly negatively associated with higher phosphorus levels and browning water at the eutrophic lakes. Furthermore, increased pH levels benefitted piscivores. Invertivore diving duck species nesting on the wetlands had declined most on sites with high alien predator indices. Large herbivorous species and species preferring oligotrophic lakes seem to be successful. We conclude that the large-scale breeding waterbird decline in Finland is closely connected to both bottom-up and top-down processes, where negative associations are emphasised especially at eutrophic lakes. Niche-, nest site- and habitat-specific management actions are required to conserve declining waterbird populations. Managing wetlands on catchments level together with alien predator control may provide important approaches to future wetland management.

Metabolic Rates of Rainbow Trout Eggs in Reconstructed Salmonid Egg Pockets

In situ evaluations of the metabolic rates (i.e., respiration and excretion) of salmonid eggs are mostly indirect, focusing on the sampling of hyporheic water from wild or artificial nests. Comparatively, experimental studies carried out under controlled, laboratory conditions are less abundant due to methodological difficulties. This study presents a novel experimental setup aimed to address this issue and enable the measurement of oxygen and dissolved inorganic nitrogen fluxes in simulated rainbow trout (O. mykiss) egg pockets. The experimental setup consists of reconstructed egg pockets in cylindrical cores under flow-through conditions. Live and dead eyed-stage eggs were incubated in a natural, sterilised gravel substrate. Hyporheic water circulation was ensured using peristaltic pumps, with the possibility to collect and analyse inflowing and outflowing water for chemical analyses. Microcosm incubations, with closed respirometry of eggs in water alone, were also carried out in order to infer the importance of microbial respiration in the simulated egg pockets. The results show an increasing trend in oxygen demand, due to the development of biofilm in the reconstructed egg pockets and increased egg respiration rates. Moreover, egg pockets showed positive ammonium net fluxes connected with the advancing developmental egg stage, while nitrate removal peaked during the last phase of the experiment, mainly due to the formation of oxic-hypoxic interfaces, leading to couple nitrification–denitrification processes. The suggested approach enables to test a number of in situ situations, including the effects of extreme hydrological conditions, sediment clogging and sudden changes in water chemistry or temperature on the survival and metabolic performances of nests, at different egg development stages.

Reservoir Drawdown Highlights the Emergent Effects of Water Level Change on Reservoir Physics, Chemistry, and Biology

AbstractWater level drawdowns are increasingly common in lakes and reservoirs worldwide as a result of both climate change and water management. Drawdowns can have direct effects on physical properties of a waterbody (e.g., by altering stratification and light dynamics), which can interact to modify the waterbody's biology and chemistry. However, the ecosystem‐level effects of drawdown remain poorly characterized in small, thermally stratified reservoirs, which are common in many regions of the world. Here, we intensively monitored a small eutrophic reservoir for 2 years, including before, during, and after a month‐long drawdown that reduced total reservoir volume by 36%. During drawdown, stratification strength (maximum buoyancy frequency) and surface phosphate concentrations both increased, contributing to a substantial surface phytoplankton bloom. The peak in phytoplankton biomass was followed by cascading changes in surface water chemistry associated with bloom degradation, with sequential peaks in dissolved organic carbon, dissolved carbon dioxide, and ammonium concentrations that were up to an order of magnitude higher than the previous year. Dissolved oxygen concentrations substantially decreased in surface waters during drawdown (to 41% saturation), which was associated with increased total iron and manganese concentrations. Combined, our results illustrate how changes in water level can have cascading effects on coupled physical, chemical, and biological processes. As climate change and water management continue to increase the frequency of drawdowns in lakes worldwide, our results highlight the importance of characterizing how water level variability can alter complex in‐lake ecosystem processes, thereby affecting water quality.

Non-negligible N2O emission hotspots: Rivers impacted by ion-adsorption rare earth mining

Rare earth mining causes severe riverine nitrogen pollution, but its effect on nitrous oxide (N2O) emissions and the associated nitrogen transformation processes remain unclear. Here, we characterized N2O fluxes from China's largest ion-adsorption rare earth mining watershed and elucidated the mechanisms that drove N2O production and consumption using advanced isotope mapping and molecular biology techniques. Compared to the undisturbed river, the mining-affected river exhibited higher N2O fluxes (7.96 ± 10.18 mmol m−2d−1 vs. 2.88 ± 8.27 mmol m−2d−1, P = 0.002), confirming that mining-affected rivers are N2O emission hotspots. Flux variations scaled with high nitrogen supply (resulting from mining activities), and were mainly attributed to changes in water chemistry (i.e., pH, and metal concentrations), sediment property (i.e., particle size), and hydrogeomorphic factors (e.g., river order and slope). Coupled nitrification-denitrification and N2O reduction were the dominant processes controlling the N2O dynamics. Of these, the contribution of incomplete denitrification to N2O production was greater than that of nitrification, especially in the heavily mining-affected reaches. Co-occurrence network analysis identified Thiomonas and Rhodanobacter as the key genus closely associated with N2O production, suggesting their potential roles for denitrification. This is the first study to elucidate N2O emission and influential mechanisms in mining-affected rivers using combined isotopic and molecular techniques. The discovery of this study enhances our understanding of the distinctive processes driving N2O production and consumption in highly anthropogenically disturbed aquatic systems, and also provides the foundation for accurate assessment of N2O emissions from mining-affected rivers on regional and global scales.

Freshwater fish otoliths record signals from both water and physiological processes: new insights from Sr/Ca and Ba/Ca ratios

Using strontium (Sr) and barium (Ba) in otoliths to determine natal origins and understand patterns of fish movements is based on the fundamental assumption that otoliths record water chemistry signals without any major alterations. Although prior studies highlighted that fish physiology can modify the water signal in otoliths, studies for freshwater fish are scarce. We exposed different groups of Atlantic salmon parr Salmo salar to different scenarios of ambient-level variations in Sr/Ca and Ba/Ca ratios and then combined otolith chemical profiles with environmental data (water chemistry and temperature), Fulton's index, and otolith growth rates to assess what factors explain/influence the elemental ratios of Sr and Ba in otoliths. Generalized additive mixed models (GAMMs) using water-based otolith composition, temperature, Fulton's index, and “individual” as explanatory variables allow to demonstrate that water chemistry alone cannot fully explain measured ratios in otoliths, except in scenarios involving significant changes in water chemistry. Other factors (physiological effects) should be accounted for reproducing short and minimal seasonal variations in water composition, considering that inter-individual variability contributes quite significantly in most scenarios.

Spatiotemporal structure and composition of the microbial communities in hypersaline Lake Magadi, Kenya

Background Soda lakes are habitats characterized by haloalkaline conditions also known to host unique microbial communities. The water chemistry changes with seasons due to evaporative concentration or floods from the surrounding grounds. However, it is not yet clear if the change in physiochemical changes influences the spatiotemporal diversity and structure of microbial communities in these ecosystems. Methods This study investigated the spatiotemporal diversity and structure of microbial communities in water and brine samples collected from hypersaline Lake Magadi in the months of June–September 2018. Amplicons were generated using Illumina sequencing of the 16S rRNA gene. Results The abundant bacterial phyla were Proteobacteria, Cyanobacteria, Bacteroidetes, Actinobacteria, Firmicutes, Verrumicrobia, Deinococcus-Thermus, Spirochaetes, and Chloroflexi. The Archaeal diversity was represented by phyla Euryachaeota, Crenarchaeota, Euryarchaeota, and Thaumarchaeota. The dominant bacterial species were: Euhalothece sp. (10.3%), Rhodobaca sp. (9.6%), Idiomarina sp. (5.8%), Rhodothermus sp. (3.0%), Roseinatronobacter sp. (2.4%), Nocardioides sp. (2.3%), Gracilimonas sp. (2.2%), and Halomonas sp. (2%). The dominant archaeal species included Halorubrum sp. (18.3%), Salinarchaeum sp. (5.3%), and Haloterrigena sp. (1.3%). The composition of bacteria was higher than that of archaea, while their richness and diversity varied widely across the sampling seasons. The α-diversity indices showed that high diversity was recorded in the month of August, followed by September, June, and July in that order. Furthermore, salinity and alkalinity affect β-diversity rather than the sampling site or seasonality. The effects of physicochemical parameters on the microbial community structure showed that temperature, pH, P+, K+, NO3 -, and total dissolved solids (TDS) had a positive correlation with the microbial community structure. Multivariate analysis revealed significant spatial and temporal effects on β-diversity and salinity and alkalinity were the major drivers of microbial composition in Lake Magadi. Conclusions We provide insights into the relationships between microbial communities and geochemistry across various sampling sites in Lake Magadi.

Impact of Climate Change on Environmental Chemistry: A Review

Environmental chemistry changed greatly with climate change, thereby influencing chemical processes in the atmosphere, hydrosphere and lithosphere. This review assessed this by examining changes in atmospheric chemistry, water chemistry, soil chemistry and biogeochemical cycles. Rising global temperatures and increased greenhouse gas emissions have changed atmospheric chemical reactions leading to alterations in air quality and the formation of secondary pollutants. Water temperature shifts and changes in water chemistry caused by climate change impacted marine biogeochemistry through ocean acidification. Nutrient cycling, soil organic matter and metal mobility were also altered as a result of soil chemistry effects. Additionally, the review focused on mitigation and adaptation strategies that involved the development of green technologies and sustainable practices for managing climate change impacts. In this analysis, environmental chemistry was emphasized as having a significant role in understanding climate change challenges through synthesis of present research works. The end also recommended further studies to be conducted while suggesting interdisciplinary approaches along with long-term monitoring needed to improve our knowledge about climate change impacts and enable policy makers take sound decisions.

Atmospheric deposition and soil water chemistry in Swedish forests since 1985 – Effects of reduced emissions of sulphur and nitrogen

Trends for the atmospheric deposition of sulphur (S) and inorganic nitrogen (inorg-N) to forests and changes in the forest soil water chemistry in Sweden have been assessed since 1985, with special focus on the last 25 years, based on measurements within the Swedish Throughfall Monitoring Network (SWETHRO). The reductions in the deposition of S and inorg-N in the southern part of Sweden corresponded relatively well with the pollutant emission reductions for S and inorg-N from both EU27 + UK and Sweden during 1996/97–2021/22. For northern Sweden the deposition of S and inorg-N decreased to a lesser extent than both European and Swedish emissions. The bulk deposition of NO3-N has decreased more than the deposition of NH4-N over the last 25-year period, which is consistent with the much larger emission reductions for NOx compared to NH3 from EU27 + UK and Sweden. The S concentrations in the soil water, at 50 cm below soil surface, have decreased during the last 25 years, however somewhat less than the S deposition. At sites with low ANC and pH in the beginning of the period, the increase in ANC was generally greater and the increase in pH was smaller, but at sites with high pH and ANC above zero, the increase in pH was dominant, in line with the nonlinear relationship between pH and ANC in the soil water. The incidence of elevated concentrations of NO3-N in the soil water was highest in southwest Sweden, ranging between 4 and 19 % of all measuring occasions since 1985/86. The reduced deposition of N over the 35-year period was not reflected in the incidence of elevated concentrations of NO3-N in the soil water over time.

Oxidation of Alloy 690 in Simulated Pressurized Water Reactor Primary Coolant – Experiments and Modeling

During normal operation of the primary loop of a water cooled-water moderated energy reactor (WWER), the associated water chemistry evolves from an initially high-boron high-potassium (beginning-of-cycle, 1200 ppm B and 8 ppm K) to significantly lower concentrations (ca. 400 ppm B and 3.5 ppm K) at the end of the respective campaign. In addition to that, the concentration of Li produced by transmutation of B reaches ca. 0.7 – 0.9 ppm. To the best of our knowledge, the effect of such water chemistry changes on pressurized water reactor (PWR) internals such as Alloy 690 have not been studied yet. Such a study appears relevant also within the frames of a discussion for a possible transition from B-Li to B-K water chemistry in PWRs.In the present paper, the effect of evolution of primary water chemistry during operation on the corrosion rate and conduction mechanism of oxide films on Alloy 690 is studied by in-situ impedance spectroscopy at 280 °C / 8 MPa during 1-week exposures in an autoclave connected to a re-circulation loop. Impedance measurements were performed in three-electrode mode featuring a Pt sheet counter electrode and a Pd electrode negatively polarized with a current of -10 µA vs. another Pt to approximate the reversible hydrogen electrode (RHE). Spectra were recorded at the corrosion potential in a frequency range 10 kHz – 0.1 mHz using an ac amplitude of 50 mV (rms). At the end of exposure, the samples were polarized in the range of potentials -0.1 to 0.5 V vs. RHE to evaluate the stability of the passive oxide. Separate samples of Alloy 690 were simultaneously exposed in the autoclave and subsequently analyzed by Glow-Discharge Optical Emission Spectroscopy (GDOES) in order to estimate the thickness and the in-depth composition of the formed oxides.Impedance data were quantitatively interpreted using the Mixed-Conduction Model for Oxide Films (MCM) to estimate the rates of metal oxidation at the alloy/oxide interface, oxide dissolution and restructuring at the film/coolant interface and ion transport in the protective layer. The effect of water chemistry evolution on corrosion rate and conduction mechanism in the oxide on Alloy 690 in primary coolant is discussed on the basis of the obtained parameters.Acknowledgments: This study is funded by the European Union-NextGenerationEU, through the National Recovery and Resilience Plan of the Republic of Bulgaria, project № BG-RRP-2.004-0002 (BiOrgaMCT).

Dynamic Monitoring of In-situ Chemical Oxidation for Remediation of Hydrocarbon Contamination with Electrical Resistivity Tomography

In situ chemical oxidation (ISCO) using persulfate, a conductive oxidant, provides a powerful signal for non-invasive geophysical techniques to characterize the remediation process of hydrocarbon contaminants. This study used ISCO for remediation in a laboratory sandbox and at an on-site contaminated site to evaluate the ability of resistivity chromatography (ERT) to monitor the process of alkali-activated persulfate remediation of hydrocarbon-contaminated soils. The experimental results show that the persulfate plume migrates mainly vertically due to density-driven flow. The relationship between resistivity and pollutant metrics further showed that pollutant depletion contributed 25.6% to the resistivity change in polluted source regions, while this contribution was less than 16% in low or non-polluted regions. In addition, field monitoring results indicate that the resistivity response is consistent with changes in water chemistry, water table, contaminant concentration and temperature. In conclusion, geophysical methods are excellent for dynamic monitoring of in situ remediation processes for hydrocarbon contamination.

Evidence of summer thermal stratification in extreme northern lakes

Rapid warming in the High Arctic has induced changes in terrestrial environments that have included major recent shifts in lakes and ponds. Numerous studies exist of spatial trends in water chemistry, bioindicator groups, and paleoenvironmental change from High Arctic lakes; however, little is known about lake thermal stratification regimes at high latitudes beyond assumptions based on generalized classification schemes. Here, we report on the presence in late July 2022 of positive thermal stratification during open-water conditions in two freshwater lakes near Clements Markham Inlet, on northern Ellesmere Island. These lakes are situated in the polar desert at 82.6°N, >1000 km north of the generally accepted northern limit of summer thermal stratification. Given their location approaching the northernmost land on Earth, the thermal profiles of these lakes suggest that the occurrence of summer stratification may no longer be discounted anywhere in the Northern Hemisphere.

DOM Associates with Greenhouse Gas Emissions in Chinese Rivers under Diverse Land Uses.

Growing evidence indicates that rivers are hotspots of greenhouse gas (GHG) emissions and play multiple roles in the global carbon budget. However, the roles of terrestrial carbon from land use in river GHG emissions remain largely unknown. We studied the microbial composition, dissolved organic matter (DOM) properties, and GHG emission responses to different landcovers in rivers (n = 100). The bacterial community was mainly constrained by land-use intensity, whereas the fungal community was mainly controlled by DOM chemical composition (e.g., terrestrial DOM with high photoreactivity). Anthropogenic stressors (e.g., land-use intensity, gross regional domestic product, and total population) were the main factors affecting chromophoric DOM (CDOM). DOM biodegradability exhibited a positive correlation with CDOM and contributed to microbial activity for DOM transformation. Variations in CO2 and CH4 emissions were governed by the biodegradation or photomineralization of dissolved organic carbon derived from autotrophic DOM and were indirectly affected by land use via changes in DOM properties and water chemistry. Because the GHG emissions of rivers offset some of the climatic benefits of terrestrial carbon (or ocean) sinks, intensified urban land use inevitably alters carbon cycling and changes the regional microclimate.

Crosslinked polyethylene (PEX) drinking water pipe: Carbon leaching, impacts on microbial growth, and developmental toxicity to zebrafish

Crosslinked polyethylene (PEX) is commonly used for building plumbing pipes, water supply connectors, dip tubes, and sometimes as buried water service lines. During periods of plumbing stagnation, drinking water chemistry and microbiology changes may occur, especially during building startup when the plumbing is new. The study objectives were to (1) characterize drinking water total organic carbon (TOC) concentration changes caused by PEX and cell growth; (2) identify compounds leached using two extraction approaches; and (3) directly measure acute and developmental toxicity effects of the PEX contact waters. A series of short- and long-term stagnation experiments were conducted. Of the three different PEX pipe brands examined, the PEX-b brand exhibited the highest organic carbon migration (24 to 120 hours range: 7.24 to 15.4 mg/L). Total cell counts increased for all three PEX types and conditions over the 120 hour exposure period at 55°C. The simulated 60-day exposure period revealed TOC levels were greater at 55°C, compared to 23°C. When zebrafish were exposed to PEX contact waters, morphological alterations (changes in zebrafish body and brain length) were observed, but no impact on survival or behavior patterns was detected. Exposure to PEX-b and PEX-c brand waters at 23°C caused a decrease in animal total body length and brain length compared to larvae in the control group. A increase in the ratio of head length to body length was observed for animals exposed to the room temperature PEX-a group, which indicates abnormal development compared to the control group. Additional studies are recommended to characterize the type and magnitude of contaminants leached and directly measure the toxicity of the resulting waters.

Long-term changes in major ion chemistry-similarities and differences between inflow rivers and the lake in Taihu watershed, China.

The major ion chemistry in the Taihu watershed has dramatically changed due to human disturbances; however, little is known about the similarities and differences in the responses of the inflow rivers and Taihu lake to the disturbances. Using historical (1950s-1970s) and recent (2018-2021) water chemistry data of inflow rivers and the lake, as well as socioeconomic and land use data, we explored the drivers for the major ion chemistry change and different responses of the inflow rivers and the receiving lake. The results indicated that, compared with 1950s-1970s, all the major ions and TDS in rivers and Taihu lake significantly increased (by 91% for Mg2+ and by 395% for Cl- in rivers; by 68% for HCO3- and 134% for Na+ in the lake); however, their increases in major ion composition presented a clear difference, i.e., although current dominant cation remained Ca in inflow rivers, the second dominant cation has shifted from Mg2+ (1950s-1970s) to Na+ (2018-2021) for rivers, while for the lake, the second dominant cation has become frequently Na+ (2018-2021), followed by Ca2+, indicating a clear salinization tendency. Furthermore, the change of some indicative ratio indices of inflow rivers and the lake in the past decades presented an apparent difference, i.e., the river systems had a higher increase rate in Ca2+/Mg2+ and SO42-/Cl- than the lake, while the lake had a higher increase in (Ca2+ + Mg2+)/HCO3-, TH/TA, and Cl-/Na+ than the river systems. Analyses indicated that increased human disturbances were the major driver for the similar increase in the TDS and major ions for both river systems and the lake, while the different algal biomass in the rivers and lake, the land use change, and declined hydrological connectivity in this watershed played important roles in the different alterations of the water chemistry indices. Comparison of major ion correlation change between the running and stagnant waters indicated a clear "lacunification" trend of inflow rivers in terms of water chemistry characteristics in this dense river-network region. Our work revealed the cause and effect of the fundamental water chemistry change in a rapid development region and will provide scientific basis for the integrated management and recovery in the watershed.

EVALUATION OF THE EFFECTS OF HEAVY METALS ON WATER FROM ILLEGAL CRUDE OIL REFINERIES: A CASE STUDY OF THREE SELECTED COMMUNITIES IN THE NIGER DELTA REGION, NIGERIA

In order to assess the levels of heavy metals and health concerns associated with the operations of illicit refineries in water, 15 surface water samples were taken from Okerenkoko, Peterou-Gbene, and Bille in the Niger Delta region of Nigeria. A number of heavy metal indices, including the Contamination Factor (Cf), Pollution Load Index (PLI), Modified Degree of Contamination (mCd), Ecological Risk Factor (Erf), and Geo Accumulation Index (Igeo), were successfully applied in the evaluation of heavy metal contamination in surface water using World Health Organization WHO (2011) and Nigerian Standard for Water Quality NSDWQ (2007) standards. Additional research from WHO and NSDWQ comparisons revealed that the majority of the investigated heavy metals were higher than permissble limits in comparison to the control site. Although the concentration of heavy metals in the aquatic habitats varies amongst the various communities in the area, according to the CV. Additionally, CV contends that there is a connection between the illicit refiners’ actions at the study site and the water chemistry changes that result in surface water contamination. According to data from the WHO and the NSDWQ, the majority of heavy metal concentration readings in the study sites exceeded the acceptable limits when compared to those in the control site. According to the results of heavy metals indices such as Cf and PLI, the surface water in the analyzed site ranges from very slightly contaminated to extremely contaminated. However, Erf and Igeo findings showed that human activities through illegal refiners increase heavy metal concentration, which results in a very high potential ecological risk associated with surface water. Additional mCd results demonstrated that in the studied sites, the surface water has a high degree of contamination. The findings suggest that surface water assessment is required to warn against a decline in water quality in the area.

Characterization of surface films that develop on pre-oxidized copper in anoxic simulated groundwater with sulphide

Surface films formed on pre-oxidized copper in anoxic simulated groundwater with sulphide were characterized by field emission gun scanning electron microscopy (FEG-SEM), Fourier transform infrared spectroscopy (FT-IR), open circuit potential (OCP) measurements, and via analysing the water chemistry and weight changes in the specimens. Additionally, films developed under identical conditions on pre-oxidized and ground copper specimens were characterized by glow discharge optical emission spectroscopy (GDOES). The results revealed that the sulphide content in the groundwater significantly influences the morphology, composition and thickness of the surface film. The build-up of Cu2S was evidenced at the sulphide contents of 32 mg/L and 320 mg/L. GDOES depth profiling revealed that sulphur and oxygen coexisted in the film all through its thickness, yet the surface was essentially rich in sulphur. The results from characterization are presented in detail in this paper and discussed from the perspective of capabilities of the used methods.

Changed mercury speciation in clouds driven by changing cloud water chemistry and impacts on photoreduction: Field evidence at Mt. Tai in eastern China

Chemical speciation of mercury (Hg) in clouds largely determines the photochemistry of Hg in the atmosphere and consequently influences Hg deposition on the surface through precipitation. Cloud water chemistry has notably changed over the last decade in response to global changes, however, the effects on Hg speciation remain poorly understood. During summer 2021, we collected sixty cloud water samples at Mt. Tai in eastern China and compared the cloud chemistry and Hg speciation with our previous findings during summer 2015. The results showed that although there were no statistically significant differences in the concentrations of total Hg (THg), dissolved Hg (DHg), and particulate Hg (PHg), there was a distinct shift in DHg species from the predominated Hg-DOM (78.6% in 2015 campaign) to the more homogeneously distributed Hg(OH)2 (28.4% in 2021 campaign), HgBr2 (26.5%), Hg-DOM (17.3%) and HgBrOH (17.0%). Changes in cloud water chemistry, particularly the significant increase in pH values to 6.49 ± 0.27 and unexpectedly high levels of bromide ions (Br−, 0.19 ± 0.22 mg L−1), were found to drive the changing of Hg speciation by enhancing Hg(II) hydrolysis and binding by Br−. Elevated Br− originating primarily from the continent likely caused noticeable differences in the dominating DHg species between cloud water sourced from marine and continental regions. The changes in chemical speciation of DHg were estimated to result in a 2.6-fold decrease in Hg(II) photoreduction rate between 2015 and 2021 campaigns (0.178 ± 0.054 h−1 vs. 0.067 ± 0.027 h−1), implying a shortened lifetime of atmospheric Hg and increased ecological risks associated with Hg wet deposition.

Response of macroinvertebrate and epilithic diatom communities to pollution gradients in Ecuadorian Andean rivers

Population growth and increasing production demands threaten the highly diverse Andean freshwater ecosystems. Biological indicators constitute a valuable tool for evaluating the ecological quality of freshwater ecosystems under different pressures. Diatom and macroinvertebrate assemblages are the most used bioindicators to assess water pollution, whereby these biotic groups occupy the first and second trophic levels and respond to habitat pollution. Several studies have explored the response of these communities to water pollution in other regions, but no studies have examined their performance in Andean rivers. In this context, this research aimed to evaluate the responses and relationships of both groups of bioindicators in the Upper Guayllabamba basin. We collected macroinvertebrate and diatom samples from nine sites in this basin during the dry and wet seasons, calculated trophic indices for both groups, and related them to environmental characteristics. The results indicated that both bioindicators were sensitive to changes in land use and nutrients. Epilithic diatoms were more sensitive to changes in water chemistry and macroinvertebrates to changes in fluvial habitat and land use. The index based on macroinvertebrates better-detected changes in quality classes between sites and seasons. Therefore, both indices gave complementary information, and their joint use seems suitable in Andean streams.

Experimental precipitation of cryogenic carbonate

Cryogenic cave carbonates (CCC) represent a specific type of speleothem precipitating from freezing water in caves. Over the past decade, considerable progress has been made concerning cryogenic calcite petrography, crystallography and geochemistry. Uncertainties remain, however, as the cave waters from which ancient cryogenic calcites form are not preserved. The present study provides an experimental approach to re-calculate the isotopic composition of the precipitating solution using CCC data. Calcium-rich bicarbonate water prepared by bubbling CO2 gas with a very low δ13C value (∼ −35 ‰) into the water was cooled under controlled laboratory conditions to account for the water chemistry changes during freezing. The experiments yielded cryogenic calcite and vaterite precipitating at temperatures of +1, +0, −0.5, −0.7, −1 and − 2 °C, with complete freezing occurring at −0.7, −1 and − 2 °C and partial freezing at −0.5 °C. The δ18Owater and δ13CDIC values, pH, electrical conductivity and alkalinity were recorded before and after the experiments. Our work documents an increase in pH, suggesting CO2 degassing eventually reaches supersaturation with calcite, leading to CaCO3 precipitation. Calcite precipitation rates are lower at the longer experiment (> 45 days). This is further confirmed by the decreasing calcite saturation index (SIcc) with time. Carbon isotope analyses of the water and carbonates revealed kinetic effects during rapid freezing. A large increase in Δ13CDIC values of the water (up to about 30 ‰) was found between the start and end of the experiments. Reasons may include CO2 degassing with increasing time leading to a markedly 13C-enriched solution. Based on our experimental data, the cryogenic crystal morphotypes are related to the precipitation sequence. Sharp-edged rhombohedra (calcite) precipitate first. Subsequently, spherulitic (vaterite) morphotypes precipitate from almost completely frozen water characterised by a high SIcc. This first experimental work dealing with cryogenic carbonate precipitates and their stable isotope composition sheds light on the origin of these peculiar speleothems and provides constraints to interpret morphologies and isotopic compositions of ancient CCCs.