Trace Metal Solubility Research Articles

Seawater flooding of calcareous soils: Implications for trace and alkaline metals mobility

Developing management strategies to safeguard public health and environmental sustainability requires a comprehensive understanding of the solubility and mobility of trace and alkaline metals in the event of seawater flooding. This study investigated the effects of seawater flooding, along the duration of flooding, on the release of trace and alkaline metals (Mn, Fe, Cu, Zn, Ca, K, and Mg) in two calcareous soils (Krome and Biscayne) located in southern Florida. Seawater flooding experiments involved two soil types and four flooding durations (1, 7, 14, and 28 days) replicated three times. Freshwater flooding experiments were also conducted for comparison. After each flooding experiment, soil samples were collected at three depths (15, 30, and 45 cm), and analyzed for selected elements. Comparative analysis revealed significant releases of Mn, Fe, and Zn in both soils flooded by seawater compared to freshwater. In most cases, significant increments were evident as early as 1-day exposure to seawater flooding, which further increased with flooding duration. However, the impacts of seawater flooding had notable differences between the two soils. Seawater flooding in Krome soil for 28 days, resulted in higher Mn, Fe, and Zn contents by 58, 340, and 510% compared with freshwater flooding, while corresponding increases in Biscayne soil were 3.3, 130, and 180%, respectively. Comparable marginal increases in Cu content were observed for both soils. Similarly, seawater flooding increased K, Mg, and Na contents from single-day flooding. The interplay between soil type, column depth, flooding duration, and their interactions proved influential factors in determining Mn, Fe, Cu, and Zn releases, with peak levels typically observed on the 28th day of flooding and at bottom depths. Overall, these findings highlight the release of these elements, raising concerns about potential plant toxicity and groundwater or surface water contamination due to leaching and runoff.

Quantitative Separation of Unknown Organic-Metal Complexes by Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry.

Dissolved organic matter (DOM) is widely recognized to control the solubility and reactivity of trace metals in the environment. However, the mechanisms that govern metal-DOM complexation remain elusive, primarily due to the analytical challenge of fractionating and quantifying metal-organic species within the complex mixture of organic compounds that comprise DOM. Here, we describe a quantitative method for fractionation and element-specific detection of organic-metal complexes using liquid chromatography with online inductively coupled plasma mass spectrometry (LC-ICP-MS). The method implements a post-column compensation gradient to stabilize ICP-MS elemental response across the LC solvent gradient, thereby overcoming a major barrier to achieving quantitative accuracy with LC-ICP-MS. With external calibration and internal standard correction, the method yields concentrations of organic-metal complexes that were consistently within 6% of their true values, regardless of the complex's elution time. We used the method to evaluate the effects of four stationary phases (C18, phenyl, amide, and pentafluoroylphenyl propyl) on the recovery and separation of environmentally relevant trace metals (Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in Suwannee River Fulvic Acid and Suwannee River Natural Organic Matter. The C18, amide, and phenyl phases generally yielded optimal metal recoveries (>75% for all metals except Pb), with the phenyl phase separating polar species to a greater extent than C18 or amide. We also fractionated organic-bound Fe, Cu, and Ni in oxidized and reduced soils, revealing divergent metal-DOM speciation across soil redox environments. By enabling quantitative fractionation of DOM-bound metals, our method offers a means for advancing a mechanistic understanding of metal-organic complexation throughout the environment.

Seasonal Variability in Fine Particulate Matter Water Content and Estimated pH over a Coastal Region in the Northeast Arabian Sea

The acidity of atmospheric particles can promote specific chemical processes that result in the production of extra condensed phases from lesser volatile species (secondary fine particulate matter), change the optical and water absorption characteristics of particles, and enhance trace metal solubility that can function as essential nutrients in nutrient-limited environments. In this study, we present an estimated pH of fine particulate matter (FPM) through a thermodynamic model and assess its temporal variability over a coastal location in the northeast Arabian Sea. Here, we have used the chemical composition of FPM (PM2.5) collected during the period between 2017–2019. Chemical composition data showed large variability in water-soluble ionic concentrations (WSIC; range: 2.3–39.9 μg m−3) with higher and lower average values during the winter and summer months, respectively. SO42− ions were predominant among anions, while NH4+ was a major contributor among cations throughout the season. The estimated pH of FPM from the forward and reverse modes exhibits a moderate correlation for winter and summer samples. The estimated pH of FPM is largely regulated by SO42− content and strongly depends on the relative ambient humidity, particularly in the forward mode. Major sources of FPM assessed based on Positive matrix factorization (PMF) and air-mass back trajectory analyses demonstrate the dominance of natural sources (sea salt and dust) during summer months, anthropogenic sources in winter months and mixed sources during the post-monsoon season.

Deposition of trace metals associated with atmospheric particulate matter: Environmental fate and health risk assessment

Anthropogenic and natural sources influence trace metals (TMs) bound to different sized particulate matter (PM) in dry and wet atmospheric deposition, which can create ecosystem and human health issues in the long run. Limited reviews are available summarizing worldwide concentrations in TMs in atmospheric PMs, their sources and pathways. Simultaneously, quantitative assessment of the potential human and ecosystem health risks imposed by the atmospheric particulate matter has not been adequately reviewed. Addressing this gap, here we review, the concentration of TMs in dry deposition mainly varies with the responsible sources, whereas, in wet deposition, it depends on the solubility of TMs. Other than deposition on impervious surfaces, the TMs incorporated PM can be deposited on biological agents. Health risk assessments show that ingestion and dermal contact pathways are more likely to cause health issues, however, the probability of occurring ingestion and dermal contact pathways is limited. Attention must be paid to the contribution from non-exhaust and exhaust vehicular emissions for TMs in atmospheric deposition, understanding their impact on stormwater management and urban agriculture. Behaviors of TMs in the atmosphere depends on many complex factors including origin, wind patterns, and weather conditions. Therefore, future research needs to be carried to model and predict the fate and transfer of TMs once they are generated through natural and anthropogenic sources. We believe that such research would allow establishing pollution control policies and measures in urban environments which will be critical to reduce the levels of TMs associated with atmospheric deposition in the environment.

Controls on groundwater selenium, arsenic and base metals in groundwater around a selenium-bearing volcanogenic massive sulfide deposit: constraints from stable isotopes, trace elements and redox controls

Understanding the controls on the behaviour of metalloids (Se, As) and metals (Cu, Zn, Pb) in natural aqueous systems is vital to interpreting hydrogeochemical data in environmental and mineral exploration applications. Geochemical, isotopic and redox measurements of a suite of groundwaters sampled from around the ABM zone of the Kudz Ze Kayah (KZK) volcanogenic massive sulfide (VMS) deposit in the Yukon, Canada are presented and contrasted with other case studies from a variety of mineral deposit types. This deposit has atypically high As (up to 4.3 wt%, average 2457 ppm) and Se (up to 2620 ppm, average 157 ppm) contents in the sulfide mineralization. As a relatively undisturbed deposit (unmined), it is an ideal site to study the mobility and solubility of trace metals in groundwaters. Herein we present field measurements (pH, dissolved oxygen, specific conductance, oxidation–reduction potential and temperature), major ion, trace element, anion (Cl, Br, SO 4 , PO 4 ), and stable isotope ( δ 2 H, δ 13 C DIC , δ 18 O, δ 18 O SO4 , δ 34 S) data. Waters are dominantly low-salinity HCO 3 to HCO 3 –SO 4 -type waters with variable sulfate (4.83 to 601 mg l −1 ), Ca (23–235 mg l −1 ) Mg (3.1–96.8 mg l −1 ), Na (0.30–66.9 mg l −1 ) and K (0.55 to 6.25 mg l −1 ) concentrations. These waters also have variable trace element concentrations that include As (0.01 to 148 µg l –1 ), Se (<0.02 to 1.01 µg l –1 ), Fe (0.01 to 3.84 mg l −1 ), Zn (<0.2 to 1070 µg l –1 ), Pb (<0.01 to 8.4 µg l –1 ), Cu (0.03 and 24.5 µg l –1 ) and Sb (0.01 to 54.4 µg l –1 ). Some waters also have elevated concentrations (compared to most meteoric waters) of Nb (up to 0.3 µg l –1 ), Y (up to 1.42 µg l –1 ), Zr (up to 18 µg l –1 ), and the rare-earth elements (REEs) ( Σ REE up to 2.04 µg l –1 ). The δ 18 O (−22.8 to −20.9 ‰) and δ 2 H (−174 to −158 ‰), together with the δ 13 C DIC (−10.6 to +1.9 ‰), δ 34 S (+10 to +12 ‰) and δ 18 O SO4 (15.5 to −4.75 ‰) all suggest that local meteoric water has interacted with massive sulfide mineralization at the ABM zone. Our results demonstrate the requirement for the use of multiple techniques in hydrogeochemical studies, with dissolved concentrations of major and trace elements coupled with a suite of stable isotopes that help define a larger geochemical footprint for the KZK deposit. Water–mineral interaction between groundwater aquifers and VMS deposits like the ABM zone are distinctly different from dispersion halos described from other deposit types (i.e. Cu porphyry, unconformity U). Thematic collection: This article is part of the Hydrochemistry related to exploration and environmental issues collection available at: https://www.lyellcollection.org/cc/hydrochemistry-related-to-exploration-and-environmental-issues

Abundance and fractional solubility of phosphorus and trace metals in combustion ash and desert dust: Implications for bioavailability and reactivity

Aerosol phosphorus (P) and trace metals derived from natural processes and anthropogenic emissions have considerable impacts on ocean ecosystems, human health, and atmospheric processes. However, the abundance and fractional solubility of P and trace metals in combustion ash and desert dust, which are two of the largest emission sources of aerosols, are still not well understood. In this study, the abundance and fractional solubility of P and trace metals in seven coal fly ash samples, two municipal waste fly ash samples, and three desert dust samples were experimentally examined. It was found that the abundance of aluminum (Al) in combustion ash was comparable or even higher than that in desert dust, and, therefore, care should be taken when using Al as a tracer of desert dust. The abundance and fractional solubility of P were higher in combustion ash, with a soluble P content ~4–6 times higher than that of the desert dust, indicating that combustion ash could be an important source of bioavailable P in the atmosphere. Except for Mn, the abundance and fractional solubility of other heavy metals were higher in the combustion ash compared to the desert dust, indicating the potential importance of combustion ash in ocean ecosystems, human health, and atmospheric processes. In contrast, both the abundance and solubility of Mn were highest in the desert dust, indicating a potentially important source of soluble Mn in the atmosphere. The fractional solubilities of P and trace metals are significantly affected by acidity and ions in the extraction solutions, and it is suggested that a buffer solution can better represent the acidity of the aqueous system in the true atmospheric environment. The results of this study improve our understanding of the sources of bioavailable and reactive P and trace metals in ambient aerosols.

Investigating trace metal precipitation in highly concentrated cell culture media with Pourbaix diagrams.

Commercial production of therapeutic proteins using mammalian cells requires complex process solutions, and consistency of these process solutions is critical to maintaining product titer and quality between batches. Inconsistencies between process solutions prepared at bench and commercial scale may be due to differences in mixing time, temperature, and pH which can lead to precipitation and subsequent removal via filtration of critical solution components such as trace metals. Pourbaix diagrams provide a useful tool to model the solubility of trace metals and were applied to troubleshoot the scale-up of nutrient feed preparation after inconsistencies in product titer were observed between bench- and manufacturing-scale batches. Pourbaix diagrams modeled the solubility of key metals in solution at various stages of the nutrient feed preparation and identified copper precipitation as the likely root cause of inconsistent medium stability at commercial scale. Copper precipitation increased proportionally with temperature in bench-scale preparations of nutrient feed and temperature was identified as the root cause of copper precipitation at the commercial scale. Additionally, cell culture copper titration studies performed in bench-scale bioreactors linked copper-deficient mammalian cell culture to inconsistent titers at the commercial scale. Pourbaix diagrams can predict when trace metals are at risk of precipitating and can be used to mitigate risk during the scale-up of complex medium preparations.

OH point defects in quartz – a review

Abstract. Research results of the past 6 decades on the incorporation of OH point defects in quartz are summarised and evaluated in terms of their application to natural samples and processes, and a link between experimental petrology, natural archives, and model calculations is made. A strong focus is put on recent studies on quartz as a rock-forming mineral, as a geochemical and/or petrological tracer, and as a tool for provenance analysis in sediments and sedimentary rocks. The most relevant defects for natural specimens are generated by coupled substitution involving mono- and trivalent cations, the most prominent being Li+, Al3+, and B3+. OH incorporation is rather a function of the availability of trace metals and water than of pressure and temperature, though temperature indirectly influences the incorporation by the solubility of trace metals in the fluid. Pressure has a negative influence on the formation of OH defects, so the most pure quartzes are probably formed in the deep crust close to the quartz/coesite transition. Natural quartz grains from the Earth's crust have on average 10 wt ppm (weight parts per million) water (5 wt ppm median), but grains with OH defect contents corresponding to up 250 wt ppm water have been discovered in sedimentary archives, matching the concentration of quartz from high-pressure experiments <4 kbar under water-saturated conditions in granitic systems. A rough division into three classes is suggested: (1) grains with pristine igneous and/or hydrothermal origin, (2) mildly thermally annealed grains, and (3) strongly dehydrated grains. While samples derived from the currently exposed Scandinavian Shield are dominated by the third class, considerable contributions of the first two classes are found in the younger rock systems in Central Europe. OH defect contents may be used to estimate mixing ratios for sediments with different sources, provided that a sufficiently large data set exists and that the different sources can be clearly distinguished by their OH inventory. Furthermore, metamorphic overprint leads to a higher degree of equilibration of OH defects between individual grains and may thus be used as a geothermometer. Finally, OH defect retention in quartz allows for estimating timescales of volcanic processes.

Clay Minerals Affect the Solubility of Zn and Other Bivalent Cations in the Digestive Tract of Ruminants In Vitro.

Simple SummaryAdverse weather conditions and harvesting technique have broad effects on forage quality including contamination with soil particles, e.g., clay minerals. Clay minerals are organised in a layered structure which enables adsorption of bivalent cations. Accordingly, ingested clay minerals may interact with dietary bivalent trace elements, such as Cu, Fe, Mn, and Zn. This study aimed to assess the relationship between clay mineral ingestion and the solubility of dietary trace elements along the digestive tract in vitro. In the presence of clay minerals, we found a reduction of solubilised Zn, Cu, and Mn under ruminal, abomasal, and duodenal conditions. However, clay minerals led to an increase in dissolved Fe under abomasal and duodenal conditions. Therefore, ingested clay minerals may be assumed to alter the solubility of essential dietary trace elements in the digestive tract of ruminants.Ruminants ingest large quantities of clay minerals along with inorganic soil constituents in roughages. The layered structure of clay minerals, however, may adsorb cations and may, thus, interfere with the ruminants’ supply of essential trace metals, such as Zn, Mn, Cu, and Fe. As quantitative knowledge about interactions between clay ingestion and essential trace metal metabolism are largely lacking, this in vitro study focussed on the effect of clay on the solubility of dietary Zn and other bivalent trace metals in the digestive tract of ruminants. Therefore, buffered rumen fluid was used for the simulation of ruminal conditions (RC), acidified rumen fluid (pH 2) was used for abomasal conditions (AC), and duodenal chyme was used for duodenal conditions (DC). These media were added with gradient levels of zinc and incubated at 39 °C for 24 h in the absence or presence of clay minerals. Soluble Zn, Cu, Mn, and Fe were derived by centrifugation (10,000× g) of incubated media, and the supernatants were analysed. Clay depressed the solubility of added Zn in ruminal (65.3% vs. 16.5%), abomasal (97.7% vs. 33.7%), and duodenal conditions (41.3% vs. 21.1%), the results of which were statistically significant (p < 0.001). Moreover, clay reduced dissolved Cu (µg/mL) (RC: 0.13 vs. 0.10; AC: 0.16 vs. 0.13; DC: 0.10 vs. 0.08) and Mn (µg/mL) (RC: 3.00 vs. 1.80; AC: 5.53 vs. 4.80; DC: 3.18 vs. 1.77) (p < 0.05 in all cases). The presence of clay minerals increased the concentrations of solubilised Fe (µg/mL) in abomasal (1.80 vs. 2.86, p < 0.05) and duodenal conditions (1.76 vs. 2.67; p < 0.05). In total, the present in vitro study demonstrates the potential of clay minerals ingested with ruminant feeds for depressing the solubility of dietary Zn, as well as the depression of dietary Cu and Mn along the passage of the digesta from the rumen until the duodenum. Additionally, clay minerals may release Fe into the digesta.

Estimation of places of production of porcelains of unknown origins excavated at the Mietsu Naval Facility site based on differences in the solubility of trace metals during the elutriation process

More than 300 porcelains of unknown origins were excavated at the Mietsu Naval Facility site in Japan in 2009, which was designated by UNESCO as a World Heritage Site in 2015. Forty-nine representative porcelain pieces were chosen and the metals in the porcelains were identified to clarify their places of production by using the synchrotron-based X-ray fluorescence method. The metal composition of porcelains was analysed by a new method designed by the authors based on the difference in the solubility of metal ions during the elutriation process carried out during the manufacturing of porcelain. Niobium (Nb) and zirconium (Zr), which are barely soluble in water, become a part of the clay, whereas rubidium (Rb), which is highly soluble in water, easily gets discharged with the upward flow of water during elutriation. The plotting of integrated fluorescence intensity ratio of Zr/Nb vs. Rb/Nb led to the porcelains being distinguished into three groups based on their places of production: Hasami, Shida, and Arita in Hizen. X-ray diffraction (XRD) patterns of the porcelains and the XRD patterns of the powdered raw pottery stones were determined. Differences in the XRD patterns are also discussed in terms of identifying the production areas of the excavated porcelains.

The control of hydrogen sulfide on benthic iron and cadmium fluxes in the oxygen minimum zone off Peru

Abstract. Sediments in oxygen-depleted marine environments can be an important sink or source of bio-essential trace metals in the ocean. However, the key mechanisms controlling the release from or burial of trace metals in sediments are not exactly understood. Here, we investigate the benthic biogeochemical cycling of iron (Fe) and cadmium (Cd) in the oxygen minimum zone off Peru. We combine bottom water and pore water concentrations, as well as benthic fluxes determined from pore water profiles and from in situ benthic chamber incubations, along a depth transect at 12∘ S. In agreement with previous studies, both concentration–depth profiles and in situ benthic fluxes indicate a release of Fe from sediments to the bottom water. Diffusive Fe fluxes and Fe fluxes from benthic chamber incubations (−0.3 to −17.5 mmol m−2 yr−1) are broadly consistent at stations within the oxygen minimum zone, where the flux magnitude is highest, indicating that diffusion is the main transport mechanism of dissolved Fe across the sediment–water interface. The occurrence of mats of sulfur-oxidizing bacteria on the seafloor represents an important control on the spatial distribution of Fe fluxes by regulating hydrogen sulfide (H2S) concentrations and, potentially, Fe sulfide precipitation within the surface sediment. Rapid removal of dissolved Fe after its release to anoxic bottom waters hints at oxidative removal by nitrite and interactions with particles in the near-bottom water column. Benthic flux estimates of Cd suggest a flux into the sediment within the oxygen minimum zone. Fluxes from benthic chamber incubations (up to 22.6 µmol m−2 yr−1) exceed diffusive fluxes (&lt;1 µmol m−2 yr−1) by a factor of more than 25, indicating that downward diffusion of Cd across the sediment–water interface is of subordinate importance for Cd removal from benthic chambers. As Cd removal in benthic chambers covaries with H2S concentrations in the pore water of surface sediments, we argue that Cd removal is mediated by precipitation of cadmium sulfide (CdS) within the chamber water or directly at the sediment–water interface. A mass balance approach, taking the contributions of diffusive and chamber fluxes as well as Cd delivery with organic material into account, suggests that CdS precipitation in the near-bottom water could make an important contribution to the overall Cd mass accumulation in the sediment solid phase. According to our results, the solubility of trace metal sulfide minerals (Cd ≪ Fe) is a key factor controlling trace metal removal and, consequently, the magnitude and the temporal and spatial heterogeneity of sedimentary fluxes. We argue that, depending on their sulfide solubility, sedimentary source or sink fluxes of trace metals will change differentially as a result of declining oxygen concentrations and the associated expansion of sulfidic surface sediments. Such a trend could cause a change in the trace metal stoichiometry of upwelling water masses with potential consequences for marine ecosystems in the surface ocean.

Evidence of Natural and Anthropogenic Impacts on Rainwater Trace Metal Geochemistry in Central Mexico: A Statistical Approach

Trace metals Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd, and As were determined on a monthly basis in a total of 52 rain samples collected from six different locations in the central region of Mexico during March 2016–April 2017. The average concentrations of trace metals (mg/L) in the rainwater samples showed an order of Zn (0.873) &gt; Fe (0.395) &gt; Mn (0.083) &gt; Cr (0.041) ≥ Cu (0.041) &gt; Pb (0.031) &gt; Ni (0.020) &gt; Co (0.013) &gt; As (0.0003) &gt; Cd (0.002). The differences observed in metal concentrations are related to variations in the influence of continental air masses, local transport, regional advection, and the solubility of trace metals. High concentrations of metals were observed in the months of March to May at all sites, probably due to the less extensive removal of air/air pollutants. The values obtained from the enrichment factor (EF) per metal showed relatively high values for Cd, Zn, Cu, Pb, Co, Ni, and Cr, suggesting anthropogenic origin. Pearson’s correlation matrix validated the distribution of trace metal sources and their relationships with local/regional meteorological characteristics. This paper presents relevant basic information for the evaluation of the toxic potential of rainwater and the possible health risks when using this source of water for human consumption.

Assessment of leaching protocols to determine the solubility of trace metals in aerosols

Atmospheric deposition of aerosols to the ocean provides an important pathway for the supply of vital micronutrients, including trace metals. These trace metals are essential for phytoplankton growth, and therefore their delivery to marine ecosystems can strongly influence the ocean carbon cycle. The solubility of trace metals in aerosols is a key parameter to better constrain their potential impact on phytoplankton growth. To date, a wide range of experimental approaches and nomenclature have been used to define aerosol trace metal solubility, making data comparison between studies difficult. Here we investigate and discuss several laboratory leaching protocols to determine the solubility of key trace metals in aerosol samples, namely iron, cobalt, manganese, copper, lead, vanadium, titanium and aluminium. Commonly used techniques and tools are also considered such as enrichment factor calculations and air mass back-trajectory projections and recommendations are given for aerosol field sampling, laboratory processing (including leaching and digestion) and analytical measurements. Finally, a simple 3-step leaching protocol combining commonly used protocols is proposed to operationally define trace metal solubility in aerosols. The need for standard guidelines and protocols to study the biogeochemical impact of atmospheric trace metal deposition to the ocean has been increasingly emphasised by both the atmospheric and oceanographic communities. This lack of standardisation currently limits our understanding and ability to predict ocean and climate interactions under changing environmental conditions.

Improved geochemical modeling of lead solubility in contaminated soils by considering colloidal fractions and solid phase EXAFS speciation

Lead (Pb) is a common contaminant in soils at e.g. mining, shooting range, and glassworks sites. In order to make reliable risk assessments and appropriate decisions on various “gentle remediation options”, such as applying phosphate, compost, or zero-valent iron to soils, the binding mechanism of Pb and its speciation needs to be known. Multi-surface geochemical equilibrium models are useful tools for estimating trace metal solubility and speciation, but for Pb the predictions are often poor. This study evaluates the recent parameterization for Pb in the Visual MINTEQ code for its ability to predict the solubility of Pb at different pH values in four historically contaminated Swedish soils. As an independent validation of the model performance, the modeled solid-phase speciation was compared to measured Pb speciation retrieved using extended X-ray absorption fine structure (EXAFS) spectroscopy. Furthermore, potential artefacts by the presence of Pb colloids were investigated by filtering solutions through both 0.45 μm and 10 kDa filters. The model accuracy for predicting Pb solubility was improved compared with previous studies producing log root mean square error (RMSE) values below 0.42 in three out of four soils, just by using generic assumptions. The use of ultrafiltered (<10 kDa) instead of the 0.45 μm-filtered Pb concentrations lowered the RMSE with ∼0.4 log units in two soils, giving a more accurate evaluation of the model performance. EXAFS proved to be a useful tool for validating and constraining the model, since the solid phase speciation did not exactly agree with the modeled results using default assumptions. However, a sample-specific optimization of the amount of “active” solid organic matter and Al + Fe hydroxides resulted in improved prediction of Pb solubility as well as better agreement with the EXAFS measurements. Solubility of Pb in the fourth, As-rich soil was probably controlled by Pb5(AsO4)3Cl (mimetite) with a solubility product constant of 10−83.53.

Predicting trace metal solubility and fractionation in Urban soils from isotopic exchangeability

Metal-salt amended soils (MA, n = 23), and historically-contaminated urban soils from two English cities (Urban, n = 50), were investigated to assess the effects of soil properties and contaminant source on metal lability and solubility. A stable isotope dilution method, with and without a resin purification step, was used to measure the lability of Cd, Cu, Ni, Pb and Zn. For all five metals in MA soils, lability (%E-values) could be reasonably well predicted from soil pH value with a simple logistic equation. However, there was evidence of continuing time-dependent fixation of Cd and Zn in the MA soils, following more than a decade of storage under air-dried conditions, mainly in high pH soils. All five metals in MA soils remained much more labile than in Urban soils, strongly indicating an effect of contaminant source on metal lability in the latter. Metal solubility was predicted for both sets of soil by the geochemical speciation model WHAM-VII, using E-value as an input variable. For soils with low metal solution concentrations, over-estimation of Cd, Ni and Zn solubility was associated with binding to the Fe oxide fraction while accurate prediction of Cu solubility was dependent on humic acid content. Lead solubility was most poorly described, especially in the Urban soils. Generally, slightly poorer estimation of metal solubility was observed in Urban soils, possibly due to a greater incidence of high pH values. The use of isotopically exchangeable metal to predict solubility is appropriate both for historically contaminated soils and where amendment with soluble forms of metal is used, as in toxicological trials. However, the major limitation to predicting solubility may lie with the accuracy of model input variables such as humic acid and Fe oxide contents where there is often a reliance on relatively crude analytical estimations of these variables.Trace metal reactivity in urban soils depends on both soil properties and the original source material; the WHAM geochemical model predicts solubility using isotopically exchangeable metal as an input.

Iron sources alter the response of Southern Ocean phytoplankton to ocean acidification

The rise in anthropogenic CO2 and the associated ocean acidification (OA) will change trace metal solubility and speciation, potentially altering Southern Ocean (SO) phytoplankton productivity and species composition. As iron (Fe) sources are important determinants of Fe bioavailability, we assessed the effect of Fe-laden dust versus inorganic Fe (FeCl3) enrichment under ambient and high pCO2 levels (390 and 900 μatm) in a naturally Fe-limited SO phytoplankton community. Despite similar Fe chemical speciation and net particulate organic carbon (POC) production rates, CO2-dependent species shifts were controlled by Fe sources. Final phytoplankton communities of both control and dust treatments were dominated by the same species, with an OA-dependent shift from the diatom Pseudo nitzschia prolongatoides towards the prymnesiophyte Phaeocystis antarctica. Addition of FeCl3 resulted in high abundances of Nitzschia lecointei and Chaetoceros neogracilis under ambient and high pCO2, respectively. These findings reveal that both the characterization of the phytoplankton community at the species level and the use of natural Fe sources are essential for a realistic projection of the biological carbon pump in the Fe-limited pelagic SO under OA. As dust deposition represents a more realistic scenario for the Fe-limited pelagic SO under OA, unaffected net POC production and dominance of P. antarctica can potentially weaken the export of carbon and silica in the future.

Solubility of aerosol trace elements: Sources and deposition fluxes in the Canary Region

African dust inputs have important effects on the climate and marine biogeochemistry of the subtropical North Atlantic Ocean. The impact of dust inputs on oceanic carbon uptake and climate is dependent on total dust deposition fluxes as well as the bioavailability of nutrients and metals in the dust. In this work, the solubility of trace metals (Fe, Al, Mn, Co and Cu) and ions (Ca, sulphate, nitrate and phosphate) has been estimated from the analysis of a long-time series of 109 samples collected over a 3-year period in the Canary Islands. Solubility is primarily a function of aerosol origin, with higher solubility values corresponding to aerosols with more anthropogenic influence. Using soluble fractions of trace elements measured in this work, atmospheric deposition fluxes of soluble metals and nutrients have been calculated. Inputs of dissolved nutrients (P, N and Fe) have been estimated for the mixed layer. Considering that P is the limiting factor when ratios of these elements are compared with phytoplankton requirements, an increase of 0.58 nM of P in the mixed layer (∼150 m depth) and in a year can be estimated, which can support an increase of 0.02 μg Chla L−1 y−1. These atmospheric inputs of trace metals and nutrients appear to be significant relative to the concentrations reported in this region, especially during the summer months when the water column is more stratified and deep-water nutrient inputs are reduced.

Temporal variability in trace metal solubility in a paddy soil not reflected in uptake by rice (Oryza sativa L.).

Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.

Trace Metal Availability and Soil Quality Index Relationships under Different Land Uses

Long-term intensive agriculture without appropriate management is likely to cause soil degradation. Therefore, monitoring of soil quality in agricultural regions is essential for protecting soil and water resources and providing high-quality and safe food. Our objective was to quantify potential soil degradation by assessing trace element solubility and other major soil properties. We used principal component analysis to select, weight, and score soil quality indicators before combining them into a soil quality index (SQI). Nineteen soil properties were quantified, but only 10 showed significant differences between forest and agricultural land uses. Four soil properties (pH, soil organic C, bulk density, and ammonium lactate extractable P) were chosen as indicators of soil quality. We found no statistical differences in overall SQI values between the two land uses, but differences in single soil properties such as soil organic C and bulk density did indicate some degradation due to agricultural practices. Trace metal availability and solubility showed no significant correlation with overall SQI values, indicating that our method for determining SQI was not a good indicator of trace metal availability and solubility.

Solubility of trace metals in two contaminated paddy soils exposed to alternating flooding and drainage

Uptake of trace metals by crops is determined by the solubility of trace metals. In paddy soils, flooding and drainage influence redox chemistry and consequently trace metal solubility and thus uptake by rice plants. Current knowledge on how the dynamics in redox chemistry affect the solubility of trace metals in contaminated paddy soils is still limited. The objectives of our study were to investigate (i) the effects of flooding and drainage on trace metal solubility in paddy soils and (ii) to what extent a multi-surface modeling approach can predict trace metal solubility under changing redox conditions. We performed a column experiment with two contaminated paddy soils with similar soil properties but contrasting pH. During two successive flooding and drainage cycles, dynamics in Eh, pH and dissolved organic matter concentrations greatly affected trace metal solubility for both soils. Multi-surface model predictions indicate that under aerobic conditions, the higher pH of the alkaline soil leads to a stronger complexation of trace metals by reactive surfaces of the soil and, consequently, to lower dissolved concentrations than in the acidic soil. Under anaerobic conditions, predictions shows that sulfide precipitates control trace metal solubility in both soils, but still the higher pH of the alkaline soil leads to lower trace metal concentrations in soil solution at equilibrium. Furthermore, model calculations showed that stoichiometry and solubility of copper sulfide minerals can substantially affect solubility of other trace metals especially when trace element concentrations exceed soil sulfate concentrations. This stoichiometry and solubility should be considered when predicting the solubility of trace metals under anaerobic conditions.