Trace Metal Speciation Research Articles

A Comparative Study on Chemical Speciation of Trace Metals as a Function of Solution pH: A Multivariate Analysis and Simulation Approach

ABSTRACT Biogeochemical activity of trace elements in the environment significantly relies on their chemical speciation. Solution pH influences the chemical speciation and biogeochemical activity of trace elements in the soil-plant continuum. The current study was conducted to simulate the influence of solution pH on chemical fractions of 11 trace elements (arsenic, lead, zinc, copper, chromium, cadmium, mercury, nickel, strontium, antimony, and selenium) using Visual Minteq, a chemical equilibrium model used for the calculation of metal speciation, sorption etc. Results delineated that pH-mediated variations in the chemical speciation of trace elements differed with their type. The results of the current study revealed a dominance of chemical trace element species at acidic (1–6), neutral (7.0), and alkaline (8–14) pH. Divalent trace elements (zinc, cadmium, copper, chromium, nickel, and lead) were the dominant species at acidic pH. However, mercury dominance has a narrow pH range (1–3), while strontium dominance has a wider pH range (1–13). Nitrate, sulfate, and phosphate fractions of trace elements also occurred at pH <8. However, at pH >8, trace elements existed in hydroxide (OH) fractions. In the case of arsenic (arsenite As3+ and arsenate As5+), selenium (selenite Se4+ and selenate Se6+), and antimony (antimonite Sb3+ and antimonate Sb5+), their dominant species get oxidized with increasing pH. Multivariate analysis was conducted for various metals for their dominance as a function of pH. Moreover, Principal Component Analysis verified a linear relation of trace element fractions with pH. Results revealed that solution pH affects the chemical fractions and the phytoavailable fraction of trace elements in growth culture and associated health hazards through soil-plant transfer.

Influence of Organic Matter and Speciation on the Dynamics of Trace Metal Adsorption on Microplastics in Marine Conditions.

Dissolved organic matter (DOM), primarily in the form of humic acid (HA), plays a crucial role in trace metal (TM) speciation and their subsequent adsorption dynamics on microplastics (MP) in aquatic environments. This study evaluates the impact of environmentally relevant concentrations of HA on the adsorption behaviors of essential (Co, Cu, Ni, and Zn) and toxic (Cd and Pb) TMs onto polyethylene (PE) and polypropylene (PP) pellets, as well as PP fibers under marine conditions, during a six-week experiment. The HA concentrations were 0.1, 1, and 5 mg/L, while all metals were in the same amounts (10 µg/L). Results reveal that HA significantly influences the adsorption of Cu, Pb, and Zn on MP, particularly on PP fibers, which exhibited the greatest TM adsorption dynamics. The adsorption patterns correspond to the concentrations of these metals in seawater, with the sequence for pellets being Zn > Cu > Pb > Ni > Co~Cd, and for fibers Cu > Zn > Pb > Co~Ni > Cd. Speciation modeling supported these findings, indicating that Cu, Pb, and Zn predominantly associate with HA in seawater, facilitating their adsorption on MP, whereas Cd, Co, and Ni mainly form free ions and inorganic complexes, resulting in slower adsorption dynamics. Statistical analysis confirmed the influence of HA on the adsorption of Cd, Pb, Cu, and Ni. By investigating the dynamics of TM adsorption on plastics, the influence of DOM on these two contaminants under marine conditions was evaluated. The presented results can help in forming a better understanding of synergistic plastic and trace metal pollution in marine systems that are relevant at the global level, since both contaminants pose a serious threat to aquatic ecosystems.

Chemical composition of indoor and outdoor PM2.5 in the eastern Arabian Peninsula

Water-soluble and trace metal species in fine particulate matter (PM2.5) were determined for indoor and outdoor environments in Doha, Qatar. During the study period, PM2.5 concentrations showed significant variability across several indoor locations ranging from 7.1 to 75.8 μg m−3, while the outdoor mass concentration range was 34.7–154.4 µg m−3. The indoor and outdoor PM2.5 levels did not exhibit statistically significant correlation, suggesting efficient building envelope protection against outdoor PM2.5 pollution. Rather than outdoor sources, human activities such as cooking, cleaning, and smoking were the most significant influence on chemical composition of indoor PM2.5. NH4+ concentration was insufficient to neutralize SO42− indoors and outdoors, indicating the predominant presence of NH4HSO4. The enrichment factors indicated that outdoor Fe, Mn, Co, Cr, and Ni in PM2.5 mostly originated from crustal sources. In contrast, the remaining outdoor trace metals (Cu, Zn, As, Cd, Pb, and V) were mainly derived from anthropogenic sources. The indoor/outdoor concentration ratios revealed significant indoor sources for NH4+ and Cu. The crustal matter, water-soluble ions, and sea salt explained 42%, 21%, and 1% of the indoor PM2.5 mass, respectively. The same groups sequentially constituted 41%, 16%, and 1% of the outdoor PM2.5 mass.

Trace metal speciation trends in Mazowe dam, Zimbabwe, a typical sub-tropical dam ecosystem impacted by gold mining and agriculture.

The present study aimed to assess trace metal speciation trends in the water and sediments of Mazowe Dam, a typical sub-tropical dam ecosystem impacted by gold mining and agriculture in Zimbabwe. The elements studied include Al, As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, and Zn. Elemental speciation in the water column was determined using Visual MINTEQ version 3.1 geochemical computer modelling, while speciation in the sediment phase was determined using sequential extraction techniques. For each element, the data obtained were subjected to extensive correlation analysis to identify intra- and inter-metal species interactions in the water column and the sediment phase, as well as across the water-sediment interface. Possible mechanisms to account for the observed species interactions are proposed. In the water column, Co was predicted to have the highest number of chemical species (9), Cd and Zn (8), Mn and Fe (7), Ni (6), Pb (5), Al and Cu (3), Cr, Hg, and As have the least (2). In the sediment, Al, As, Co, Cr, Cu, Fe, Ni and Fe mainly exist in the residual fraction, while Zn and Mn concentrations in fractions vary per sampling site, with no fraction that is dominant across the sampling sites. Equilibrium exchange reactions across the water-sediment interface were observed e.g., for Cd species /FA2Cd (aq) and Co species /FACo+2G (aq), and /FA2Co (aq). This study is valuable in highlighting trace metal speciation in a tropical dam ecosystem in Africa and adds to the growing knowledge about the behaviour of trace metals in aquatic ecosystems in the region and globally.

Adsorption of trace metals onto different plastics during long-term exposure in an estuarine environment: Influence of time, stratified water column, and specific surface area

The pervasive increase of plastics in marine systems and subsequent trace metals (TM) adsorption represents a critical environmental challenge. This long-term study is first to investigate how duration of exposure and stratified water column impact TM adsorption on various plastics in an estuary. We exposed polypropylene (PP), polyethylene (PE), poly(ethylene terephthalate) (PET), and fluorinated ethylene propylene (FEP) to estuarine conditions, categorizing them into three distinct groups to capture diverse human activities: pre-production pellets (Pellets), single-use plastics (SUP) and laboratory plastics (Lab). Plastic and water samples were analyzed before deployment and 1, 4, 7 and 16 months after deployment at three depths in the stratified Krka River estuary (Croatia). We measured TM concentrations, pH and salinity in the water column, and adsorbed TM amounts on plastics. Additionally, we examined plastic sample surfaces by Raman spectroscopy and scanning electron microscopy. TM speciation was modeled from water column data to better explain adsorption processes. Statistical analysis indicates that Zn, Cd, Pb, Ni, and Co adsorption depends on both duration of exposure and stratified water column, while Cu is influenced solely by duration of exposure to estuarine environment. Adsorbed TM amounts varied significantly among the plastic groups (Pellets, SUP and Lab), but not among different polymer types (PP, PE, PET and FEP). A noteworthy observation was the difference in the results of statistical analysis when investigating TM amounts expressed by plastic sample mass and by plastic sample surface area. Results expressed by plastic sample mass showed a difference between SUP group versus Pellets and Lab groups, while results expressed by plastic sample surface area distinguished Pellets group compared to other two groups. Therefore, we suggest presenting TM adsorption results in similar studies both by plastic sample mass and by plastic sample surface area. This approach will improve the understanding of TM adsorption on plastics, and enable more effective comparisons among the scientific literature dealing with plastics of different specific surface areas.

Ocean alkalinity enhancement using sodium carbonate salts does not lead to measurable changes in Fe dynamics in a mesocosm experiment

Abstract. The addition of carbonate minerals to seawater through an artificial ocean alkalinity enhancement (OAE) process increases the concentrations of hydroxide, bicarbonate, and carbonate ions. This leads to changes in the pH and the buffering capacity of the seawater. Consequently, OAE could have relevant effects on marine organisms and in the speciation and concentration of trace metals that are essential for their physiology. During September and October 2021, a mesocosm experiment was carried out in the coastal waters of Gran Canaria (Spain), consisting on the controlled variation of total alkalinity (TA). Different concentrations of carbonate salts (NaHCO3 and Na2CO3) previously homogenized were added to each mesocosm to achieve an alkalinity gradient between Δ0 to Δ2400 µmol L−1. The lowest point of the gradient was 2400 µmol kg−1, being the natural alkalinity of the medium, and the highest point was 4800 µmol kg−1. Iron (Fe) speciation was monitored during this experiment to analyse total dissolved iron (TdFe, unfiltered samples), dissolved iron (dFe, filtered through a 0.2 µm pore size filter), soluble iron (sFe, filtered through a 0.02 µm pore size filter), dissolved labile iron (dFe′), iron-binding ligands (LFe), and their conditional stability constants (KFeL′) because of change due to OAE and the experimental conditions in each mesocosm. Observed iron concentrations were within the expected range for coastal waters, with no significant increases due to OAE. However, there were variations in Fe size fractionation during the experiment. This could potentially be due to chemical changes caused by OAE, but such an effect is masked by the stronger biological interactions. In terms of size fractionation, sFe was below 1.0 nmol L−1, dFe concentrations were within 0.5–4.0 nmol L−1, and TdFe was within 1.5–7.5 nmol L−1. Our results show that over 99 % of Fe was complexed, mainly by L1 and L2 ligands with kFe′L′ ranging between 10.92 ± 0.11 and 12.68 ± 0.32, with LFe ranging from 1.51 ± 0.18 to 12.3 ± 1.8 nmol L−1. Our data on iron size fractionation, concentration, and iron-binding ligands substantiate that the introduction of sodium salts in this mesocosm experiment did not modify iron dynamics. As a consequence, phytoplankton remained unaffected by alterations in this crucial element.

Extended ADM1 model to study trace metal speciation and its effects on anaerobic digestion

Trace metals (TM) are often added to anaerobic digestors (AD) to improve digestor performance and methane yield. Though numerous experimental studies are done to study TM effects, a model based on ADM1 will help plant operators in case of metal deprivation as there are analytical limitations in quantifying metal speciation which controls TM effects on AD. This study developed a complete dynamic model based on ADM1 with least and unavoidable model input information to study TM speciation and its influence on AD. In addition to the biochemical and gas stripping processes described in ADM1, the model introduced new physicochemical processes with effects of operational conditions like pH, temperature and ionic strength. The biogeochemical processes influencing TM speciation include microbial uptake, precipitation (sulphides, phosphates, carbonates), adsorption (onto biomass, soluble inerts and precipitates), inorganic complexation and organic complexation (with EDTA, VFAs, amino acids (AAs)). The model was tested under different scenarios: variable EDTA concentration and dosing form, variable substrate and variable ionic strength. Complexation of TMs with EDTA and AAs influences metal bioavailability and methane yield. Supplementing EDTA reduces TM dosing and dosing EDTA as metal-EDTA complex is more effective than supplementing metals and EDTA separately. TM-AA complexation depends on substrates as amino acid compounds vary with substrates. Ionic strength influences TM adsorption and precipitation processes and hence is an important operational parameter controlling the system like pH and temperature. The model has been compared to experimental data obtained from this study and has been successfully applied to predict cobalt deprivation in an anaerobic digestor.

The importance of the soluble and colloidal pools for trace metal cycling in deep-sea pore waters

Physical and chemical trace metal speciation are important for our understanding of metal cycling and potential toxicity to marine life. Trace metals can behave differently in diffusion processes or particle-solution interactions and have different bioavailabilities depending on their physical and chemical forms, which often depend on redox conditions. Here we investigated dissolved (&amp;lt; 0.2 µm) and soluble (&amp;lt; 0.02 µm) concentrations of Mn, Co, Ni, Fe, Cu, V, Mo, U, Cd, and As in oxic and suboxic deep-sea sediments of the central equatorial Pacific Ocean. Vanadium, Mo, U, As, and Cd showed no significant concentration differences between their dissolved and soluble forms, suggesting that they are present as inorganic ionic species or organic complexes in the truly dissolved or small colloidal fraction. In contrast, the colloidal fraction (&amp;gt; 0.02 µm &amp;lt; 0.2 µm) of Mn, Co, Ni, and Cu increased with depth in oxic pore waters and Fe had the largest but variable colloidal pool. Soluble Mn, Co, and Ni were released in the uppermost 2-4 cm in the sediment because of reductive dissolution. The increasing colloidal fraction with depth suggests a decrease in the concentration of small organic ligands with depth, that are abundant in the surface sediment pore waters, and instead an increasing importance of larger (&amp;gt; 0.02 µm) inorganic nanoparticles and colloids such as Mn and Fe (oxyhydr)oxides that control Mn, Fe, and Co cycling at depths &amp;gt; 10 cm. The distribution of Ni and Cu cannot be exclusively explained by inorganic nanoparticles and a shift from low to larger high molecular weight organic ligands might occur. These findings provide new insights into trace metal distributions in the dissolved phase, highlighting the diversity of metal complexes and the need to incorporate these in future calculations of benthic metal fluxes and ecotoxicity assessments, especially in oxic pore waters.

Trace metal partitioning in the parnaíba delta in dry season, equatorial coast of Brazil

Trace metal concentrations in the particulate fractions (MP), dissolved fractions (MD) and sediments (MS), such as Ba, Cu, Co, Cr, Pb, Ni and Zn, were determined during the dry season of the largest open sea delta of Americas, the Parnaíba River Delta (Brazil). This study aimed to comprehend the distribution, dynamic changes of metal speciation and environmental quality index of trace metals in the particulate fractions and subsurface sediments in scenario of major marine influence over the delta. The trace metals bound to suspended particulate material (SPM) from weathering the drainage basin exhibited a removal trend under increases in salinity and pH. Desorption influenced the partitioning of BaMP, ZnMP, NiMP, CoMP, CuMP, and the adsorption and precipitation of PbMP and CrMP to the surface sediments. The organic matter contents in the sediments acts as an important geochemical carrier of these contaminants, and the dissolved organic carbon influences the binding of PbMD in the subsurface waters. The geoaccumulation index (Igeo) plays a crucial role in revealing potential contamination with ZnMP contents and weak association to this fraction. These results make possible the assessment of ecological risk by metal contamination and global pollution mitigation in coastal tidal estuaries under intensive physical mixing along the equatorial coast.

Patricia Smichowski, a researcher who works hard to contribute to science, kindly granted BrJAC an interview

Patricia Smichowski is a Licentiate in Chemistry (equivalent to a Master in Science) of the University of Buenos Aires. She obtained an MS in Nuclear Engineering from the Engineering School of the University of Buenos Aires in 1981 and received her Ph.D. in chemistry in 1995 from the Complutense University, Madrid, Spain. In 1982, she joined the Argentine Atomic Energy Commission (CNEA) where she is currently Head of the Analytical Developments Division. She is also Principal Researcher at the National Council of Scientific and Technical Research (CONICET). She specializes in the development and application of atomic spectrometric techniques to environmental and biological analysis. Her interests lie in the preconcentration, speciation, and determination of trace metals and metalloids in a variety of matrices by employing plasma-based techniques, atomic fluorescence spectrometry, and other coupled techniques. She has conducted national and international projects aimed at characterizing the presence of metals, metalloids, ions, and organic compounds in airborne particulate matter, as well as elucidating their origin. She holds a patent, with other researchers, relating to the development of a sorbent for arsenic retention. Patricia Smichowski has published 130 peer reviewed articles and 12 book chapters, given 45 invited lectures at international meetings, and has co-organized several international conferences. She is a member of the advisory board of four international analytical chemistry journals, as well as the European Virtual Institute for Speciation Analysis.

New Insights into the Organic Complexation of Bioactive Trace Metals in the Global Ocean from the GEOTRACES Era

The GEOTRACES program has greatly expanded measurements of dissolved trace metal concentrations across ocean basins, but to understand the behavior and cycling of metals and their impacts on primary productivity, we must understand the chemical forms in which they are present in the environment. Organic ligands play a central role in the speciation and cycling of trace metals in the marine environment, controlling their chemical reactivity and bioavailability. Here, we present an overview of the contributions the GEOTRACES program has made to understanding ocean metal speciation through advancing our knowledge of the distribution, sources, and sinks of metal-binding organic ligands across the global ocean, particularly for iron. Detailed assessments and intercalibration of the speciation methods most commonly applied have allowed integration of metal-binding ligand measurements across datasets. Work to characterize specific ligand groups within the wider pool of dissolved organic matter, along with their sources and sinks, is starting to unravel the role of metal-binding organic ligands in global biogeochemical cycles. Recent advances in complementary analytical techniques using liquid chromatography and mass spectrometry present a molecular picture of metal speciation and bioavailability—and also pose new questions. Moving forward, we need to address knowledge gaps in our understanding of how metal speciation and complexation relates to bioavailability in order to recognize the impacts of ocean metal distributions and cycling on marine productivity and the global carbon cycle.

Complex Speciation and Distribution of Iron, Sulfur, and Trace Metals in Coal Mine Soils Reflect Grain- and Sub-Grain-Scale Heterogeneity during Pyrite Oxidative Dissolution

Historical coal mining practices have caused various soil and water hazards, particularly through the dumping of mine waste. The primary environmental risk associated with this waste is the leaching of toxic metals from dumps of spoil or refuse into the subsurface soil or into nearby water resources. The extent of metal release is controlled via the oxidative dissolution of pyrite and potential re-sequestration through secondary Fe oxides. The characterization of the dominant Fe-bearing phase and the distribution of trace metals associated with these phases was determined via electron microscopy, synchrotron-based X-ray micro-fluorescence (μ-XRF) element and redox mapping from shallow mine soils from an impacted watershed in Appalachian Ohio. The dominant Fe-bearing phases were: (1) unweathered to partially weathered pyrite; (2) pseudomorphic replacement of pyrite with Fe(III) oxides; (3) fine-grained Fe oxide surface coatings; and (4) discrete Fe(III) oxide grains. Thicker secondary coatings and larger particles were sulfate rich, whereas smaller grains and thinner coatings were sulfate poor. The discrete Fe oxide grains exhibited the highest concentrations of Cr, Mn, Ni, and Cu, and sub-grain-scale concentration trends (Mn &gt; Cr &gt; Ni &gt; Cu) were consistent with bulk soil properties. Predicting future metal transport requires an understanding of metal speciation and distribution from the sub-grain scale to the pedon scale.

Distribution of copper-binding ligands in Fram Strait and influences from the Greenland Shelf (GEOTRACES GN05)

The Fram Strait represents the major gateway of Arctic Ocean waters towards the Nordic Seas and North Atlantic Ocean and is a key region to study the impact of climate change on biogeochemical cycles. In the region, information about trace metal speciation, such as copper, is scarce. This manuscript presents the concentrations and conditional stability constants of copper-binding ligands (LCu and log KcondCu2+L) in the water column of Fram Strait and the Greenland shelf (GEOTRACES cruise GN05). Cu-binding ligands were analysed by Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) using salicylaldoxime (SA) as competitive ligand. Based on water masses and the hydrodynamic influences, three provinces were considered (coast, shelf, and Fram Strait) and differences were observed between regions and water masses. The strongest variability was observed in surface waters, with increasing LCu concentrations (mean values: Fram Strait = 2.6 ± 1.0 nM; shelf = 5.2 ± 1.3 nM; coast = 6.4 ± 0.8 nM) and decreasing log KcondCu2+L values (mean values: Fram Strait = 15.7 ± 0.3; shelf = 15.2 ± 0.3; coast = 14.8 ± 0.3) towards the west. The surface LCu concentrations obtained above the Greenland shelf indicate a supply from the coastal environment to the Polar Surface Water (PSW) which is an addition to the ligand exported from the central Arctic to Fram Strait. The significant differences (in terms of LCu and log KcondCu2+L) between shelf and coastal samples were explained considering the processes which modify ligand concentrations and binding strengths, such as biological activity in sea-ice, phytoplankton bloom in surface waters, bacterial degradation, and meltwater discharge from 79NG glacier terminus. Overall, the ligand concentration exceeded those of dissolved Cu (dCu) and kept the free copper (Cu2+) concentrations at femtomolar levels (0.13–21.13 fM). This indicates that Cu2+ toxicity limits were not reached and dCu levels were stabilized in surface waters by organic complexes, which favoured its transport to the Nordic Seas and North Atlantic Ocean and the development of microorganism.

Bioavailable iron concentrations regulate phytoplankton growth and bloom formation in low-nutrient lakes

The growth of phytoplankton in lakes is thought to be primarily controlled by macronutrient concentrations, but the availability of trace metal micronutrients, such as iron (Fe), are increasingly recognised as important regulators of lake primary production. This study evaluates the role of Fe in regulating phytoplankton growth in lakes of different nutrient status in New Zealand. The results of this unique year-long study, combining highly sensitive trace metal concentration analysis of waters and particulates with advanced trace metal bioavailability and speciation modelling, constrains thresholds for bioavailable Fe and colloidal Fe of 0.8 nmol·L−1 and 30 nmol·L−1, respectively, below which phytoplankton growth-limitation occurs. These thresholds specifically control diatom bloom formation and termination in lakes, thereby exerting a strong influence on freshwater carbon sequestration, given the dominance of diatoms in lake bloom assemblages. Importantly, potentially toxic cyanobacteria thrived only after events of bottom water anoxia, when additional dissolved Fe in concentrations ≥4 nmol·L−1 was released into the water column. These new thresholds for bioavailable and colloidal Fe offer the potential to manage micronutrient levels in lakes for the purpose of regulating algal bloom formation and carbon sequestration, while at the same time, suppressing the formation of harmful cyanobacterial blooms.

Metabolic Regulation of Copper Toxicity during Marine Mussel Embryogenesis.

The development of new tools for assessing the health of cultured shellfish larvae is crucial for aquaculture industries to develop and refine hatchery methodologies. We established a large-volume ecotoxicology/health stressor trial, exposing mussel (Perna canaliculus) embryos to copper in the presence of ethylenediaminetetraacetic acid (EDTA). GC/MS-based metabolomics was applied to identify potential biomarkers for monitoring embryonic/larval health and to characterise mechanisms of metal toxicity. Cellular viability, developmental abnormalities, larval behaviour, mortality, and a targeted analysis of proteins involved in the regulation of reactive oxygen species were simultaneously evaluated to provide a complementary framework for interpretative purposes and authenticate the metabolomics data. Trace metal analysis and speciation modelling verified EDTA as an effective copper chelator. Toxicity thresholds for P. canaliculus were low, with 10% developmental abnormalities in D-stage larvae being recorded upon exposure to 1.10 μg·L-1 bioavailable copper for 66 h. Sublethal levels of bioavailable copper (0.04 and 1.10 μg·L-1) caused coordinated fluctuations in metabolite profiles, which were dependent on development stage, treatment level, and exposure duration. Larvae appeared to successfully employ various mechanisms involving the biosynthesis of antioxidants and a restructuring of energy-related metabolism to alleviate the toxic effects of copper on cells and developing tissues. These results suggest that regulation of trace metal-induced toxicity is tightly linked with metabolism during the early ontogenic development of marine mussels. Lethal-level bioavailable copper (50.3 μg·L-1) caused severe metabolic dysregulation after 3 h of exposure, which worsened with time, substantially delayed embryonic development, induced critical oxidative damage, initiated the apoptotic pathway, and resulted in cell/organism death shortly after 18 h of exposure. Metabolite profiling is a useful approach to (1) assess the health status of marine invertebrate embryos and larvae, (2) detect early warning biomarkers for trace metal contamination, and (3) identify novel regulatory mechanisms of copper-induced toxicity.

Dynamic modelling the effects of ionic strength and ion complexation on trace metal speciation during anaerobic digestion

Dosing trace metals into anaerobic digestors is proven to improve biogas production rate and yield by stimulating microorganisms involved in the metabolic pathways. Trace metal effects are governed by metal speciation and bioavailability. Though chemical equilibrium speciation models are well-established and widely used to understand metal speciation, the development of kinetic models considering biological and physicochemical processes has recently gained attention. This work proposes a dynamic model for metal speciation during anaerobic digestion which is based on a system of ordinary differential equations aimed to describe the kinetics of biological, precipitation/dissolution, gas transfer processes and, a system of algebraic equations to define fast ion complexation processes. The model also considers ion activity corrections to define effects of ionic strength. Results from this study shows the inaccuracy in predicting trace metal effects on anaerobic digestion by typical metal speciation models and the significance of considering non-ideal aqueous phase chemistry (ionic strength and ion pairing/complexation) to define speciation and metal labile fractions. Model results show a decrease in metal precipitation and increase in metal dissolved fraction and methane production yield with increase in ionic strength. Capability of the model to dynamically predict trace metal effects on anaerobic digestion under different conditions, like changing dosing conditions and initial iron to sulphide ratio, was also tested and verified. Dosing iron increases methane production and decreases hydrogen sulphide production. However, when iron to sulphide ratio is greater than 1, methane production decreases due to increase in dissolved iron which reaches inhibitory concentration levels.

Ocean acidification increases copper accumulation and exacerbates copper toxicity in Amphioctopus fangsiao (Mollusca: Cephalopoda): A potential threat to seafood safety

Ocean acidification (OA) and trace metal pollutants coexist to exert combined effects on the functions and services of marine ecosystems. Increasing atmospheric carbon dioxide has caused a decrease in the pH of the ocean, affecting the bioavailability and speciation of trace metals and consequently altering metal toxicity in marine organisms. As an important trace metal functioned in hemocyanin, the richness of Copper (Cu) in octopuses is remarkable. Therefore, the biomagnification and bioaccumulation capacities of Cu in octopuses may be a non-negligible risk of contamination. Here, Amphioctopus fangsiao was continuously exposed to acidified seawater (pH 7.8) and copper (50 μg/L) to investigate the combined effect of ocean acidification and Cu exposure on marine mollusks. Our results showed that A. fangsiao could adapt well to ocean acidification after 21 days of the rearing experiment. However, the accumulation of Cu in A. fangsiao intestine increased significantly in acidified seawater under high levels of Cu stress. In addition, Cu exposure can influence the physiological function of A. fangsiao, including growth and feeding. This study also demonstrated that Cu exposure disturbed glucolipid metabolism and induced oxidative damage to intestine tissue, and ocean acidification further exacerbated these toxic effects. The obvious histological damage and microbiota alterations were also caused by Cu stress and its combined effect with ocean acidification. At the transcription level, we found numerous differentially expressed genes (DEGs) and significantly enriched KEGG pathways, involving glycolipid metabolism, transmembrane transport, glucolipid metabolism, oxidative stress, mitochondrial, protein and DNA damage, all revealing the strong toxicological synergetic effect of Cu and OA exposure and the molecular adaptation mechanism of A. fangsiao. Collectively, this study demonstrated that octopuses may withstand future ocean acidification conditions, however, the complex interactions of future OA and trace metal pollution need to be emphasized. OA can influence the toxicity of trace metals, inducing a potential threat to marine organism safety.

Chemical Speciation and Leaching of Trace Metals in Groundwater from the Depleted Landfills, India

Abstract The poor groundwater quality through the leaching of contaminants from depleted landfill is a concern to the scientific community. Therefore, the role of landfills on groundwater quality cannot be neglected in an urban area. The factors influencing the leaching of trace metals in groundwater are soil profile, geochemical and environmental condition of disposed of refuse materials, groundwater-table depth, and climatic factors. This research work delineates landfill role in contaminating groundwater through the chemical speciation of trace metals. Analyzed groundwater quality data indicate most of the samples were classified under Ca2+-Na+ type cation and Cl- type of anion hydrogeochemical facies. The investigations of the mineral equilibrium indicate equilibrium with silicate minerals, which favors kaolinite formation. Saturation index indicates that hematite, goethite, chrysotile, dolomite, ferric-hydroxide, hydro-xyapatite, jarosite-K, cerussite, vivianite, and willemite are reactive minerals in the aquifer water and control their hydrogeochemistry. The study of chemical speciation of trace metals indicates the high possibility of oxidation-reduction, ion-exchange, and chemical-weathering reaction mechanism, which causes the release of trace metal ions and further contaminated aquifer water through leaching. It also justifies through study of contaminant movement in vertical profile of the soil. The chemical speciation of trace metals indicates a reducing atmosphere in the aquifer due to the dominance of Fe2+, Mn2+, Zn2+, Pb2+, and Cu2+ ions in aquifer water. Mn2+ and Zn2+ concentration decreases with depth, while Fe2+ and Pb2+ ion concentration low in the middle layer of the aquifer indicate the contribution through anthropogenic input since it is not available in geology of study area.

Electroanalytical Trace Metal Cations Quantification and Speciation in Freshwaters: Historical Overview, Critical Review of the Last Five Years and Road Map for Developing Dynamic Speciation Field Measurements.

An historical overview covering the field of electroanalytical metal cations speciation in freshwaters is presented here, detailing both the notable experimental and theoretical developments. Then, a critical review of the progress in the last five years is given, underlining in particular the improvements in electrochemical setups and methodologies dedicated to field surveys. Given these recent achievements, a road map to carry out on-site dynamic metal speciation measurements is then proposed, and the key future developments are discussed. This review shows that electroanalytical stripping techniques provide a unique framework for quantitatively assessing metals at trace levels while offering access to both thermodynamic and dynamic features of metal complexation with natural colloidal and particulate ligands.

ISIDORE, a Probe for In Situ Trace Metal Speciation Based on the Donnan Membrane Technique and Electrochemical Detection Part 2: Cd and Pb Measurements during the Accumulation Time of the Donnan Membrane Technique

The Donnan membrane technique (DMT), in which a synthetic or natural solution (the "donor") is separated from a ligand-free solution (the "acceptor") by a cation-exchange membrane, is a recognized technique for measuring the concentration of a free metal ion in situ, with coupling to electrochemical detection allowing for the quantification of the free metal ion directly on site. However, the use of the DMT requires waiting for the free metal ion equilibrium between the donor and the acceptor solution. In this paper, we investigated the possibility of using the kinetic information and showed that non-equilibrium experimental calibrations of Cd and Pb with the ISIDORE probe could be used to measure free metal concentrations under conditions of membrane-controlled diffusion transport. The application of this dynamic approach made it possible to successfully determine the concentration of free Cd in synthetic and natural river samples. Furthermore, it was found that the determination of free Cd from the slope was not affected by the Ca concentration ratio between the acceptor and donor solution, as opposed to the traditional approach based on Donnan equilibrium. This ISIDORE probe appears to be a promising tool for determining free metal ions in natural samples.