Labile Concentrations Research Articles

A new simple index for characterizing the labile heavy metal concentration in soil by diffusive gradients in thin films technique

Diffusive gradients in thin films technique (DGT) is recognized as a more reliable method for determining labile heavy metal (HM) concentration in soil than traditional destructive methods. However, the current DGT measurement index, CDGT, theoretically underestimates the true labile concentration (Clabile) of HMs in soil and lacks direct comparability with the conventional soil HM content indices due to unit differences. Here, we proposed CDGT-W, a new simple index which is defined as the HM accumulation in the binding layer, normalized to the weight of soil (optimized water content = 100% of the maximum water holding capacity) filled in the open cavity-type DGT device over a specified deployment time (optimized time = 24 h). The procedure for measuring CDGT-W is analogous to that of CDGT but includes precise determination of water content (water/dry soil) and the mass of soil filled in the cavity. We conducted measurements of Cu, Pb, Cr(Ⅵ) and As(V) as CDGT-W, CDGT, solution concentration (Csoln), and CaCl2 extractable concentration (CCaCl2) on three soils with a diverse range of HM concentrations. CDGT-W showed significant linear correlations with all other tested indexes. The ratios of CDGT-W to CCaCl2 varied between 0.30 and 0.98 for all HM–soil combinations with only one exception, a range much greater than CDGT/Csoln (typically <0.1) but lower than 1. This suggested that CDGT-W may more accurately reflect Clabile than CDGT (theoretically underestimates Cliable) and CCaCl2(likely overestimates Cliable). Additionally, CDGT-W measurements for these four HMs exhibited a broad measure concentration range and a low detection limit (mg/kg level). Consequently, CDGT-W may offer a more reliable alternative to CDGT for characterizing Clabile in unsaturated soils.

In situ, high-resolution evidence for the release of heavy metals from lake sediments during ice-covered and free periods

Heavy metal dynamics at the sediment-water interface (SWI) has attracted plenty of attention due to their meticulous depiction for metal sorption-release processes. However, little is known about their concentration, migration and release characteristics underneath the ice, especially at the millimeter scale. Here we investigated dynamics of labile As, Cd, Cu, Mn, Pb and Zn by the diffusive gradients in thin-films (DGT) technique during ice-covered and ice-free periods in the Lake Xingkai basin. The concentrations of metals were relatively high at the SWI and ranged for As: 0.001~13.42 μg L−1, Cd: 0.01~0.45 μg L−1, Cu: 0.001~2.75 μg L−1, Mn: 5.31~2958.29 μg L−1, Pb: 0.06~1.43 μg L−1, and Zn: 2.92~112.96 μg L−1. Particularly, concentration of Mn was extremely higher than other studies, possibly due to diagenetic process. Labile concentrations of heavy metals in January were significantly lower than those in May, suggesting that elevated temperatures lead to the release of heavy metals from the sediment to the overlying water. Based on the Fick’s first law, the diffusive fluxes as a source of Mn (413.82-1163.25 mg·m-2·d-1) and As (3.53 -8.12 mg·m-2·d-1) indicated that heavy metals were released from sediments to the overlying water. While the diffusive fluxes as a sink of Zn (-1.80-(-2.36) mg·m-2·d-1) and Pb (-0.02-(-0.46) mg·m-2·d-1) to sediments. Redundancy Analysis (RDA) revealed that the main factors influencing the heavy metal migration were dissolved oxygen (45.6% of total explanation, P=0.01) in January, and water temperature (52.9%, P=0.006) in May. This study extends theoretical scope for understanding metal migration and release process, and provides valuable suggestions for lake management during the freezing period.

Application of Diffusive Gradients in Thin-films (DGT) for assessing the heavy metals mobility in soil and prediction of their transfer to Russula virescens

Although edible mushrooms are considered a source of many beneficial nutrients for human, they can also represent a risk to health due to their capacity to accumulate heavy metals. In this study, the total dissolved in soil solution and labile concentrations of heavy metals (Cd, Pb, Cu, Zn, Co, Cr, Mn, Ni, and Fe) in soil were measured and correlated with their concentrations accumulated in Russula virescens wild mushrooms. The diffusive gradient in thin films (DGT) technique was used to measure the labile metals content in the soil (CDGT), and corroborated with the metals concentrations in soil solution (Csoln) was used to calculate an R-value, which can estimate the metals resupply from soil solid phase when they are uptake by mushroom. The DGT-labile metal concentrations decreased in the order Mn > Fe > Zn > Cu > Co > Ni > Cd ≅ Pb > Cr. The R-values, calculated as the ratio between CDGT and Csoln decreased in the order: Cd (0.50) > Zn (0.37) > Pb (0.33) > Cu (0.24) ≅ Ni (0.24) ≅ Co (0.23) > Mn (0.16) > Fe (0.12) > Cr (0.04). For the first time, we compared the R-values with the bioaccumulation factors (BAFs) in mushrooms, and it was observed that, a similar increasing trend of BAFs with the R-values exists, thus the capacity of the soil solid phase to fast re-supply metals to soil solution increases BAFs. Although the soil samples were not contaminated with heavy metals above the legislative limits, the concentrations of heavy metals accumulated in mushrooms were high enough to pose risks for humans, mainly for children, due to their Cu content.

Occurrence, source identification and ecological risk assessment of heavy metals in water and sediments of Uchalli lake – Ramsar site, Pakistan

Uchalli Lake is an internationally significant Ramsar site that needs protection for supporting migratory birds. The current study aimed to assess wetland health by examining water and sediments utilizing total and labile heavy metals concentration, pollution indices, ecological risk assessment, water recharge and pollution induction sources through isotope tracer techniques. Al concentration in water was of serious concern as it was 440 times higher than the maximum acceptable concentration of Environmental Quality Standard of the UK for aquatic life in saline waters. Labile concentration predicted very severe enrichment of Cd, Pb, and moderate enrichment of Cu. Modified ecological risk index predicted very high ecological risk in sediments. The δ 18O, δ2H and D-excess values indicate that the lake was mainly recharged by local meteoric water. Enriched values of δ 18O and δ2H suggest a high evaporation of lake water, making lake sediments more enriched with metals. Isotopic and D-excess values of groundwater suggest a quick rainwater recharge to groundwater around the Uchalli Lake. Nitrates isotopes indicate that the rainwater runoff is main source of induction of fertilizers, pesticides and soil bonded metals in the lake system. The lake is recharged by rainwater runoff, from catchment areas, that erode the soil particles and agricultural residual waste dumped in the lake.

A new approach to using Diffusive Gradient in Thin-films (DGT) labile concentration for Water Framework Directive chemical status assessment: adaptation of Environmental Quality Standard to DGT for cadmium, nickel and lead

Integrative passive samplers, such as DGT (Diffusive Gradients in Thin-films), are identified in European Technical Guidance Documents as promising tools to improve the quality of the assessment, in the context of the WFD (EU Water Framework Directive). However, DGT results cannot yet be used directly in a regulatory framework to assess the chemical status of water bodies, as DGT labile concentrations cannot be directly compared to the metal AA-EQSmarine water (Annual Average Environmental Quality Standard) established by the WFD, which are defined in the dissolved concentration. Therefore, prior to using DGT results in a regulatory context, for cadmium, nickel and lead, an adaptation of existing AA-EQSmarine water for DGTs should be pursued, ensuring at least the same level of protection. In this sense, in the framework of the MONITOOL project, a robust database of dissolved and labile metal concentrations in transitional and coastal waters, for adapting the existing AA-EQSmarine water for DGT technique, was obtained. Building on these results, this study proposes a methodology and provides values and equations for using DGT results for the chemical status assessment of marine waters, by adapting the EQSmarine water to adapted EQSDGT or predicting dissolved concentrations from DGT results. Based on available dataset, a first simulation of “chemical status” assessment per MONITOOL sampling site using DGT measured labile concentrations was carried out and the results were compared to an assessment based on dissolved concentration to check their compliance. These results demonstrate that the use of DGT passive samplers is appropriate for the metal concentrations level encountered in the marine environment. Further work is recommended to test the effectiveness of the methodology proposed in this study under WFD conditions on more sites and to establish common strategy guidelines for the use of DGT passive samplers in monitoring.

Effect of tree species and substrate properties on organic phosphorus forms in afforested Technosols

AbstractPlanted vegetation is considered one of the most important soil‐forming factors in the reclamation of degraded post‐mining lands for forestry. The objective of this study was to compare the effect of N‐fixing tree species and non‐N‐fixing tree species on the organic phosphorus (Porg) forms in technosols developing from various substrates. Samples were taken from the uppermost layer (depth 0–5 cm) of technosols afforested with black locust (Robinia pseudoacacia), black alder (Alnus glutinosa), silver birch (Betula pendula), and scots pine (Pinus sylvestris). Samples of the tree foliage and the O‐horizons were taken as well. The studied technosols developed from Quaternary sands (sands), fly ashes after lignite combustion (ashes), and Miocene clays (clays). The soil samples were measured for the contents of labile (POlab) and moderately labile organic phosphorus (POmod), phosphorus contained in fulvic and humic acids (Pfulv and Phum, respectively), and residual organic phosphorus (POres). The foliage and O‐horizon samples were measured for the concentrations of C, N, and P. The N‐fixing tree species had higher P concentration in their foliage than non‐N‐fixing tree species. However, in the O‐horizon, the highest P concentration was determined under birch and not under N‐fixers. The effect of tree species on the organic P (Porg) concentrations in the mineral soil was limited with significantly lower Porg concentrations under pine. The soil under this species contained less Pfulv, Phum, and POres. However, the percentages of POlab, POmod, Pfulv, Phum, and POres in soil Porg were nearly the same under all tree species. The largest effect on the Porg concentration and the contents of particular Porg fractions was from the substrate type. Sands contained much less Porg than the clays and ashes, but their percentage of POlab in Porg was much higher than in the two other substrates. We conclude that N‐fixing trees do not affect the concentration of labile organic P, and the major factor controlling this Porg fraction is the soil substrate quality.

Simultaneous determination of heavy metal concentrations and toxicities by diffusive gradient in thin films containing Acinetobacter whole-cell bioreporters (Bio-DGT)

Heavy metal contaminations may cause severe toxic impacts to ecological systems and human health. Measurements of metals' bioavailable concentrations and toxicities simultaneously and in-situ in environments can advance the understanding of their hazardous effects. The diffusive gradients in thin-films (DGT) is an in-situ technique can measure metal speciation and labile concentrations, but cannot yet provide the direct toxicity information. The whole-cell bioreporter Acinetobacter baylyi ADPWH_recA was successfully incorporated into the DGT device to develop a novel technique, Bio-DGT, for assessing the toxicity of metals at the same time of measuring their labile concentrations. The bioassay used in Bio-DGT can sense the mixture toxicity from multiple contaminants and the DGT can assist in identifying which toxicants may be causing the toxicity. Cadmium was used as the model metal to test the performance of Bio-DGT in waters and soils. The masses of Cd accumulated in Bio-DGT increased linearly and theoretically with time for 7 days deployment, indicating little influences from bioreporter cells on DGT performance. A positive relationship between bioluminescent signals towards Cd demonstrated the sensitive and active bioreporters' response. The sensitive of Bio-DGT, indicated by Cd concentrations causing the response, is 0.01 mg/L. The stable response from Bio-DGT under various conditions (pH 4–8, ionic strengths 0.01–0.5 M) and 30 days storage time suggest the applicability of the technique in real environments. The deployment of Bio-DGT in contaminated soils demonstrated that Cd toxicity was regulated by labile concentration, showing its potential application for the risk assessment of heavy metal contaminations, and its further feasibility in using Bio-DGT for measuring integration of multiple contaminants’ effects and simultaneously determine the main toxicity driver(s).

A simple, green and low-cost agarose-based binding layer for simultaneous determination of cations and anions in aquatic systems using DGT.

The diffusive gradients in thin films (DGT) technique pre-concentrates labile species of trace elements, giving time-integrated in situ information about their labile concentrations. All previous DGT approaches for simultaneous uptake of cations and anions have used the hazardous polyacrylamide reagent to immobilize the binding phase. The present work proposes a diffusive layer of agarose and a mixed binding layer of ZrO2 and Chelex 100 immobilized in an agarose hydrogel to simultaneously determine the labile concentration of cations (Mn, Co, Ni, Cu, Zn and Cd) and anions (V, As, Se, Mo and Sb) in aquatic systems. The use of both layers using agarose instead of carcinogenic polyacrylamide as the hydrogel significantly reduces the costs and simplifies the manufacturing process. The proposed device was evaluated through recovery tests, deployment curves and pH/ionic strength tests. The mixed binding layer was compared with commercially available DGT devices for in situ deployment in river water. The relationships between accumulated mass and time (24 h) was linear (r2 > 0.9) for all analytes. The diffusion coefficients obtained were consistent with the literature, ranging from 3.98 to 8.43 × 10-6 cm2 s-1. Except for Zn at pH 8.0, the obtained values of CDGT/Cbulk were within the range of 1.00 ± 0.2 for the studied range of pH and for most ionic strengths. However, at low ionic strength, the concentrations of Mn, Co, Ni, Zn, V and Mo were underestimated. The concentrations of trace elements determined in river water using the proposed devices agreed with the labile concentrations determined by using commercial devices.

Soil properties influence the toxicity and availability of Zn from ZnO nanoparticles to earthworms

To develop models that support site-specific risk assessment for nanoparticles (NPs), a better understanding of how NP transformation processes, bioavailability and toxicity are influenced by soil properties is needed. In this study, the influence of differing soil properties on the bioavailability and toxicity of zinc oxide (ZnO) NPs and ionic Zn to the earthworm Eisenia fetida was investigated. Earthworms were exposed to ZnO_NPs and ionic Zn, between 100 and 4400 mg Zn/kg, in four different natural soils (organic matter content: 1.8–16.7%, soil pH: 5.4–8.3, representing sandy loam to calcareous soils). Survival and reproduction were assessed after 28 and 56 days, respectively. Zn concentrations in soil pore waters were measured while labile concentrations of Zn were measured using an in-situ dynamic speciation technique (diffusive gradient in thin films, DGT). Earthworm Zn tissue concentrations were also measured. Soil properties influenced earthworm reproduction between soil controls, with highest reproductive output in soils with pH values of 6–7. Toxicity was also influenced by soil properties, with EC50s based on total Zn in soil ranging from 694 to >2200 mg Zn/kg for ZnO_NP and 277–734 mg Zn/kg for ionic Zn. Soil pore water and DGT measurements showed good agreement in the relative amount of Zn extracted across the four soils. Earthworms exposed to ZnO_NPs survived higher Zn concentrations in the soils and had higher tissue concentrations compared with ionic Zn exposures, particularly in the high organic content calcareous soil. These higher tissue concentrations in ZnO_NP exposed earthworm could have consequences for the persistence and trophic mobility of Zn in terrestrial systems and need to be further investigated to elucidate if there any longer-term risks associated with sustained input of ZnO_NP to soil.

Distribution of organophosphate ester fractions in sediment of the Eastern China Marginal Seas and the influencing factors.

Organic pollutant fractions should be closely investigated because of their different ecological risks. In this study, we examined the distribution of organophosphate ester (OPE) fractions (labile, stable-adsorbed, and tight-adsorbed fractions) in sediments from Eastern China Marginal Seas (ECMSs) and assessed the influencing factor of the fractions. The mean values of total OPEs in ECMSs are 13.70 ± 6.16μg L-1 in seawater and 32.04 ± 14.31μgkg-1 in sediment. The results showed that OPE concentration decreased from the northern to the southern ECMSs, and tris(1-chloro-2-propyl) phosphate and tris(1,3-dichloro-2-propyl) phosphate were the primary OPEs. The mean contents of labile, stable-adsorbed, and tight-adsorbed fractions in the ECMSs were 9.50, 11.29, and 11.71μgkg-1, respectively. Labile OPEs were predominant in offshore waters; the percentage of stable- and tight-adsorbed fractions increased progressively with offshore distance in ECMSs. The specific surface area and surface functional groups of sediment were not consistent with the fraction concentrations from the correlation coefficient, but the gross domestic product per coastline agreed well with the fraction distribution. Based on this, we conclude that human activity, rather than physicochemical characteristics of sediments, may be the primary influencing factor of the relative distribution of different OPE concentration fractions in ECMSs.

Combining DGT with bioaccessibility methods as tool to estimate potential bioavailability and release of PTEs in the urban soil environment

Potentially toxic elements (PTEs) in urban soil environments pose a noticeable risk to both ecosystem and human health; however, only a fraction of the elemental content is available for biota. To better know the potential risk of PTEs in the urban soil environment, geochemical fractionation, bioaccessibility, and potential bioavailability of four PTEs (Cd, Cu, Pb, and Zn) were investigated by the combined use of different methods. The results showed that a high non-residual chemical fraction is related to a high bioavailability of the selected elements. The ranges of labile concentration of Cu, Zn, Cd and Pb in all sampling sites measured by diffusive gradients in thin films (DGT) were 3.5–18.0, 14.2–26.5, 0.09–1.0, and 1.8–15.7 μg/L, respectively. The high non-residual contents pointed out a serious hazard to the urban environment. The bioaccessible concentrations in gastric and lung phases were closely positively correlated with DGT-measured content (r = 0.63–0.99, p < 0.05), suggesting the potential use of DGT for the prediction of PTEs risk to human health. Moreover, the correlation of DGT results with the soluble and reducible fractions of PTEs may allow DGT use for quick screenings of the PTEs fraction potentially mobilizable during flooding events in urban soil environments. Our study suggests that combing DGT, bioaccessibility and biogeochemical fractionation could provide a more accurate assessment of the urban environmental quality and be helpful for pollution control and urban planning.

Calibration Spiking of MIR-DRIFTS Soil Spectra for Carbon Predictions Using PLSR Extensions and Log-Ratio Transformations

There is a need to minimize the usage of traditional laboratory reference methods in favor of spectroscopy for routine soil carbon monitoring, with potential cost savings existing especially for labile pools. Mid-infrared spectroscopy has been associated with accurate soil carbon predictions, but the method has not been researched extensively in connection to C lability. More studies are also needed on reducing the numbers of samples and on how to account for the compositional nature of C pools. This study compares performance of two classes of partial least squares regression models to predict soil carbon in a global (models trained to data from a spectral library), local (models trained to data from a target area), and calibration-spiking (spectral library augmented with target-area spectra) scheme. Topsoil samples were+ scanned with a Fourier-transform infrared spectrometer, total and hot-water extractable carbon determined, and isometric log-ratio coordinates derived from the latter measurements. The best RMSEP was estimated as 0.38 and 0.23 percentage points TC for the district and field scale, respectively—values sufficiently low to make only qualitative predictions according to the RPD and RPIQ criteria. Models estimating soil carbon lability performed unsatisfactorily, presumably due to low labile pool concentration. Traditional weighing of spiking samples by including multiple copies thereof in training data yielded better results than canonical partial least squares regression modeling with embedded weighing. Although local modeling was associated with the most accurate predictions, calibration spiking addressed better the trade-off between data acquisition costs and model quality. Calibration spiking with compositional data analysis is, therefore, recommended for routine monitoring.

Mycelium chemistry differs markedly between ectomycorrhizal and arbuscular mycorrhizal fungi

The chemical quality of soil carbon (C) inputs is a major factor controlling litter decomposition and soil C dynamics. Mycorrhizal fungi constitute one of the dominant pools of soil microbial C, while their litter quality (chemical proxies of litter decomposability) is understood poorly, leading to major uncertainties in estimating soil C dynamics. We examined litter decomposability of arbuscular mycorrhizal (AM) and ectomycorrhizal (EM) fungal species using samples obtained from in vitro cultivation. We showed that the chemical composition of AM and EM fungal mycelium differs significantly: EM fungi have higher concentrations of labile (water-soluble, ethanol-soluble) and recalcitrant (non-extractable) chemical components, while AM fungi have higher concentrations of acid-hydrolysable components. Our results imply that differences in decomposability traits among mycorrhizal fungal guilds represent a critically important driver of the soil C cycle, which could be as vital as is recognized for differences among aboveground plant litter.

Source tracing with cadmium isotope and risk assessment of heavy metals in sediment of an urban river, China

The Nanfei River was one of dominant inflowing rivers of the fifth largest freshwater Chaohu Lake in China, which had been subjected to increasing nutrients and contaminants from population expansion, rapid industrialization and agricultural intensification in recent decades. In present study, surface sediment from the Nanfei River was collected to investigate the anthropogenic impact on distribution and bioavailability of heavy metals. Possible Cd sources along the river were constrained by using Cd isotope signatures and labile concentrations of heavy metals in sediment were determined through the DGT technique for risk assessment. Results showed that Cd in river sediment showed greatest enrichment (EF 0.8–9.4), indicating massive pollution from anthropogenic activities. Among the various possible Cd source materials, urban road dust, industrial soil and chicken manure, displayed higher Cd abundance and enrichment that might contribute to Cd accumulation in river sediment. Cadmium isotopic composition in river sediment was ranged from −0.21 ± 0.01‰ to 0.13 ± 0.03‰, whereas yielded relative variation from −0.31 ± 0.02‰ to 0.23 ± 0.01‰ in source materials. Accordingly, Cd sources along the river were constrained, i.e. traffic and industrial activities in the upper and middle reaches whereas agricultural activities in the lower reaches. Furthermore, the evaluation on ecological risk of heavy metals in sediment on basis of SQGs and DGT-labile concentrations demonstrated that Pb and Zn might pose higher risk on aquatic species. The present study confirmed that Cd isotopes were promising source tracer in environmental studies.

Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides.

Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II)aq). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III)labile) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III)labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2-1.0 mM Fe(II)aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution-reprecipitation mechanism mediated by Fe(III)labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. A linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III)labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

Plant litter composition and stable isotope signatures vary during decomposition in blue carbon ecosystems

The ratio of isotopes of carbon (13C:12C or δ13C) and nitrogen (15N:14N or δ15N) are common indicators of the flow and storage of organic matter in coastal wetland research. Effective use of these indicators requires quantification and understanding of: (1) the variability of isotope signatures of potential organic matter source materials; and (2) the influence of organic matter decomposition on isotopic signatures. While it is well-established that organic matter characteristics change during the decomposition process, there has been little direct quantification of any concurrent shifts in isotope signatures for coastal detritus. In this study, we addressed this by quantifying: (1) shifts in sample composition using solid-state 13C Nuclear Magnetic Resonance (NMR) spectroscopy; and (2) shifts in δ13C and δ15N signatures of coastal plant tissues from field litterbag experiments. We observed significant shifts in 13C NMR spectra across the course of deployment for all four plant tissues assessed (leaves of mangrove Avicennia marina; branchlets of supratidal tree Casuarina glauca; leaf wrack and roots/rhizomes of the seagrass Zostera muelleri), driven largely by the preferential loss of labile constituents and concentration of more resistant macromolecules, such as lignin and leaf waxes. While there were shifts in isotope ratios for all species, these varied in direction and magnitude among species, tissue type and isotopes. This included δ13C enrichments of up to 3.1‰ and 2.4‰ in leaves of A. marina, and branchlets of C. glauca, respectively, but δ13C depletions of up to 4.0‰ for Z. muelleri. Shifts in δ15N varied among species and tissue types, with few clear temporal patterns. Partial least squares regression analyses showed that some tissue isotope signatures can be reliably predicted on the basis of sample composition (13C NMR spectra), however, multiple inter- and intra-species variations preclude a simple explanation of isotopic signature shifts on the basis of plant-material molecular shifts alone. Further, we cannot preclude the potential influence of microbe-associated organic matter on sample composition or isotopic signatures. Our findings emphasise the importance of considering decomposition effects on stable isotope signatures in blue carbon ecosystems. Isotope approaches will remain a valuable tool in coastal ecosystem research, but require robust experimental approaches (including appropriate use of decomposed end-members or fractionation correction factors; quantification of microbial organic matter) and quantification of decomposition dynamics for specific plant tissues and environmental settings.

Assessment of dissolved mercury by diffusive gradients in thin films devices in abandoned ponds impacted by small scale gold mining

In order to fulfil the Minamata Convention on Mercury, it is necessary to monitor the Hg contamination in freshwater ecosystems nearby artisanal and small scale gold mining (ASGM) areas. Since most of these ASGM communities are located in remote areas, a convenient method for sampling, preserving and transporting samples is needed. In this study we evaluated the feasibility of the diffusive gradient in thin-films (DGT) technique to detect and quantify the labile fraction of Hg and other metals (Pb, Cu, Zn, Cd, Ni, Mn and Cr) in a hard-to-reach gold mining district in the state of Chocó, Colombia. We deployed DGT at sampling sites along the Atrato river and abandoned mining ponds (AMPs) which were deserted in different periods since 1997 to 2019 (6–15 years). In average, the labile THg concentrations in AMPs (148.9 ± 43.2 ng L−1) were a 50% higher than in the river water (99.9 ± 37.4 ng L−1). In the ponds, no significant differences were found in labile Hg with respect abandonment period. Labile Ni (0.9–493.1), Mn (1.33–11.48), Cu (0.030–2.233), and Zn (0.67–10.29) (in μg L−1) were found in higher amounts than for the rest of metals. Labile concentrations of metals are related with their downstream proximity to gold mining activities, being higher in devices deployed close to ASGM sites. Moreover, this study demonstrates the feasibility of the DGT technique to sample, transport, storage, and preserve labile Hg from hard-to-reach ASGM areas.

WaterQuality Guidelines for Metal Contaminants in Stormwater Runoff: Insights and Considerations.

WaterQuality Guidelines for Metal Contaminants in Stormwater Runoff: Insights and Considerations.

Lability and bioavailability of Co, Fe, Pb, U and Zn in a uranium mining restoration site using DGT and phytoscreening.

Mine restoration is a long and ongoing process, requiring careful management, which must be informed by site-specific, geochemical risk assessment. Paired topsoil and tree core samples from 4 sites within the uranium mining complex of INB Caldas in Minas Gerais (Brazil) were collected. Soil samples were analysed for their total content of Co, Fe, Pb, U and Zn by XRF, and subsequently, the potential environmental bioavailability of these metals were investigated by DGT and pore water analysis. In addition, results were compared with metal concentrations obtained by Tree Coring from the forest vegetation. In all sampling areas, mean total concentrations of U (Ctot. = 100.5 ± 66.5 to 129.6 ± 57.1 mg kg-1), Pb (Ctot. = 30.8 ± 12.7 to 90.8 ± 90.8 mg kg-1), Zn (Ctot. = 91.5 ± 24.7 to 99.6 ± 10.3 mg kg-1) and Co (Ctot. = 73.8 ± 25.5 to 119.7 ± 26.4 mg kg-1) in soils exceeded respective quality reference values. Study results suggest that AMD caused the increase of labile concentrations of Zn in affected soils. The high lability of the elements Pb (R = 62 ± 34 to 81 ± 29%), U (R = 57 ± 20 to 77 ± 28%) and Zn (R = 21 ± 25 to 34 ± 31%) in soils together with high bioconcentration factors found in wood samples for Pb (BCF = 0.0004 ± 0.0003 to 0.0026 ± 0.0033) and Zn (BCF = 0.012 ± 0.013 to 0.025 ± 0.021) indicated a high toxic potential of these elements to the biota in the soils of the study site. The combination of pore water and DGT analysis with Tree Coring showed to be a useful approach to specify the risk of metal polluted soils. However, the comparison of the results from DGT and Tree Coring could not predict the uptake of metals into the xylems of the sampled tree individuals.

Modelling of long-term Zn, Cu, Cd and Pb dynamics from soils fertilised with organic amendments

Abstract. Soil contamination by trace elements (TEs) is a major concern for sustainable land management. A potential source of excessive inputs of TEs into agricultural soils are organic amendments. Here, we used dynamic simulations carried out with the Intermediate Dynamic Model for Metals (IDMM) to describe the observed trends of topsoil Zn (zinc), Cu (copper), Pb (lead) and Cd (cadmium) concentrations in a long-term (&gt;60-year) crop trial in Switzerland, where soil plots have been treated with different organic amendments (farmyard manure, sewage sludge and compost). The observed ethylenediaminetetraacetic acid disodium salt (EDTA)-extractable concentrations ranged between 2.6 and 27.1 mg kg−1 for Zn, 4.9 and 29.0 mg kg−1 for Cu, 6.1–26.2 mg kg−1 for Pb, and 0.08 and 0.66 mg kg−1 for Cd. Metal input rates were initially estimated based on literature data. An additional, calibrated metal flux, tentatively attributed to mineral weathering, was necessary to fit the observed data. Dissolved organic carbon fluxes were estimated using a soil organic carbon model. The model adequately reproduced the EDTA-extractable (labile) concentrations when input rates were optimised and soil lateral mixing was invoked to account for the edge effect of mechanically ploughing the trial plots. The global average root mean square error (RMSE) was 2.7, and the average bias (overestimation) was −1.66, −2.18, −4.34 and −0.05 mg kg−1 for Zn, Cu, Pb and Cd, respectively. The calibrated model was used to project the long-term metal trends in field conditions (without soil lateral mixing), under stable climate and management practices, with soil organic carbon estimated by modelling and assumed trends in soil pH. Labile metal concentrations to 2100 were largely projected to remain near constant or to decline, except for some metals in plots receiving compost. Ecotoxicological thresholds (critical limits) were predicted to be exceeded presently under sewage sludge inputs and to remain so until 2100. Ecological risks were largely not indicated in the other plots, although some minor exceedances of critical limits were projected to occur for Zn before 2100. This study advances our understanding of TEs' long-term dynamics in agricultural fields, paving the way to quantitative applications of modelling at field scales.