Bioavailability Of Pollutants Research Articles

Evaluation of two contrasted activated carbon-based sequestration strategies to reduce soil-bound chlordecone bioavailability in piglets.

Chlordecone (Kepone) (CLD) is a highly persistent pesticide formerly used in the French West Indies. High levels of this pesticide are still found in soils and represent a subsequent source of contamination for outdoor-reared animals which may ingest involuntary non negligible amounts of soil. In that context, sequestering matrices like activated carbons (ACs) may be used to efficiently decrease the bioavailability of such organic pollutants. The present study intends to assess the respective efficiency of two sequestering strategies where two different ACs were provided either via feed incorporation or via soil amendment. This study involved 20 piglets randomly distributed into 5 experimental groups (4 replicates). All groups were exposed to 10 μg of CLD per kg of BW per day during 10 days via a contaminated soil. In both "Soil-ACs" treatment groups, the contaminated soil was amended by 2% (mass basis) of one of the two ACs. The two "Feed-ACs" groups received the contaminated soil and one dough ball containing 0.5% (mass basis) of one of the ACs. The piglets were then euthanized before collection of pericaudal adipose tissue and the whole liver and CLD analysis. A significant decrease of CLD concentrations in liver and adipose tissue was observed only in the "Soil-ACs" groups in comparison with the control group (P < 0.001). This decrease was particularly important for the coconut shell activated carbon where relative bioavailability was found lower than 1.8% for both tissues.

Effects of carbon nanotubes on biodegradation of pollutants: Positive or negative?

Recently, a large quantity of carbon nanotubes (CNTs) enters the environment due to the increasing production and applications. More and more researches are focused on the fate and possible ecological risks of CNTs. Some literatures summarized the effects of CNTs on the chemical behavior and fate of pollutants. However, little reviewed the effects of CNTs on the biodegradation of pollutants. In general, the effects of CNTs on the biodegradation of pollutants and the related mechanisms were summarized in this review. CNTs have positive or negative effects on the biodegradation of contaminants by affecting the functional microorganisms, enzymes and the bioavailability of pollutants. CNTs may affect the microbial growth, activity, biomass, community composition, diversity and the activity of enzymes. The decrease of the bioavailability of pollutants due to the sorption on CNTs also causes the reduction of the biodegradation of contaminants. In addition, the roles of CNTs are controlled by multiple mechanisms, which are divided into three aspects i.e., properties of CNTs, environment condition, and microorganisms themself. The better understanding of the fate of CNTs and their impacts on the biochemical process in the environment is conducive to determine the release of CNTs into the environment.

Assessment of remediation potential of flora of the Southern Urals

Soil degradation caused by human activities currently remains one of the most important environmental problems. Phytoremediation is a group of technologies for environmental clean-up and soil restoration by plants. The level of soil contamination, the bioavailability of pollutants, as well as the accumulation of metals by the plant are crucial for phytoremediation. Currently, it seems relevant to study representatives of the herbaceous flora typical for the region from the point of view of accumulation of pollutant metals. For the study we selected 5 sites located in different areas of Orenburg city. The plots estimated the content of total and active forms of heavy metals in the soil. On the study sites, samples were taken from plants during the growing season. The study analyzed the biomass of 11 plant species from 5 families and 8 elements. As a result of a comparative analysis obtained, the paper presents calculated correlation coefficients (R) between the indicators of the concentration of heavy metals in the soil and plants from the point of view of the accumulation efficiency of Pb and Cd. Plants-phytoremediators accumulate Pb from inactive soil forms – Cichorium intybus L. (R2=0.72 at P<0.05) and Polygonum aviculare L. (R2=0.57 at P<0.05). Plant accumulating Pb due to the absorption of its active forms – Arctium lappa L. (R2=0.4 at P<0.01). Promising phytoremediators of available forms of Cd – Polygonum aviculare L. (R2=0.65 at P<0.05) and Plantago media L. (R2=0.55 at P<0.05).

Microplastics modify the toxicity of glyphosate on Daphnia magna

Plastic contamination is an environmental problem spreading to even the most remote aquatic and terrestrial habitats and in particular, microplastics represent an uncertain threat for organisms. Microplastics can have a direct negative effect, but they can also potentially modify the toxicity and bioavailability of pollutants. Here, we tested over 1 week the combined effect of three different glyphosate chemical formulations (glyphosate acid, glyphosate-monoisopropylamine salt, and Roundup Gran) and two types of microplastics (polyethylene (PE) microbeads and polyethylene terephthalate/polyamide (PET/PA) fibers), on Daphnia magna. Glyphosate-monoisopropylamine salt caused the highest mortality after 1 week exposure (23.3%), whereas glyphosate acid the lowest (12.5%), when tested in the absence of microplastics. These results were inverted, however, when the individuals were exposed in combination with the PE microbeads (glyphosate acid: 53.3% and glyphosate-monoisopropylamine salt: 18.3%) or the PET/PA fibers (glyphosate acid: 30.0% and glyphosate-monoisopropylamine salt: 8.3%). The mortality in the Roundup Gran formulation also increased when combined with the two microplastics, though the effect was less pronounced. In all experiments, the effect of the treatments and time was significant, though there was no significant interaction between them. In most treatments, negative effects were not observed after 48 h or later. The change in toxicity of the glyphosate formulations caused by microplastics can be linked to the different sorption properties of the glyphosate-based chemicals formulations. The outcome of this study highlights that beside the potential direct negative effects of microplastics, they can modify the toxicity of pollutants, such as herbicides.

Implementing standardized desorption extraction into bioavailability-oriented bioremediation of PAH-polluted soils

We applied a standardized desorption extraction method (Tenax extraction), to assess the bioavailability of native polycyclic aromatic hydrocarbons (PAHs) present in contaminated soils. Single-time point Tenax extraction at 20 h has been recently proposed by the International Organization for Standardization as one of the chemical methods to measure environmental bioavailability of nonionic pollutants (ISO/TS 16751). This work is one of the first ones that use this ISO method systematically in the field of bioremediation, and shows its advantages when used in combination with total concentrations determined with conventional, exhaustive solvent extraction. This method has been applied to different PAHs contaminated soils which had a different level of total PAHs (66–4370 mg kg−1) and which were from different contaminated sites and dissimilar bioremediation approaches. In most samples the study was focused on phenanthrene and benzo(a)pyrene as representative pollutants, although the profile of total PAHs was also studied in some samples. The results from this study show that the pollutant fractions extracted with Tenax during 20 h (D20) decreased after traditional bioremediation (biostimulation and phytoremediation), but they often increased in bioavailability-oriented treatments involving either biosurfactants or bioaugmentation with specialized microbial inocula. Therefore, D20-based assessments provided information on the bioremediation performance, not directly evident through the measurement of total PAH concentrations.

Toxicity and Mechanisms of Action of Polycyclic Aromatic Hydrocarbon Pollution in Red Algae (Gracilaria corticata) from the Northern Coast of the Oman Sea.

The activities of selected biomarkers including 7-ethoxycoumarin-O-deethylase (ECOD) and glutathione S-transferase (GST) were measured in the red algae (Gracilaria corticata) obtained from the Oman Sea. Chemical analyses were used to assess the polycyclic aromatic hydrocarbons (PAHs) in the red algae. Total PAH concentrations in the red algae ranged from 3.61 to 8.14 ng g-1 dry weight. Mean GST and ECOD activity also varied from 8.87 to 15.32 nmol/mg protein/min and from 0.31 to 1.02 pmol/min/mg protein, respectively. Significant correlations were found between the total PAH levels and the selected biomarkers (p < 0.01). The results showed that ECOD and GST enzymes reacted to PAHs in phase I and II detoxification mechanisms of red algae (G. corticata), which extend the use of these biomarkers for investigation of the biological effects of PAH pollution as well as determination of pollution bioavailability. Environ Toxicol Chem 2019;38:1947-1953. © 2019 SETAC.

Environmental and Agricultural Relevance of Humic Fractions Extracted by Alkali from Soils and Natural Waters.

To study the structure and function of soil organic matter, soil scientists have performed alkali extractions for soil humic acid (HA) and fulvic acid (FA) fractions for more than 200 years. Over the last few decades aquatic scientists have used similar fractions of dissolved organic matter, extracted by resin adsorption followed by alkali desorption. Critics have claimed that alkali-extractable fractions are laboratory artifacts, hence unsuitable for studying natural organic matter structure and function in field conditions. In response, this review first addresses specific conceptual concerns about humic fractions. Then we discuss several case studies in which HA and FA were extracted from soils, waters, and organic materials to address meaningful problems across diverse research settings. Specifically, one case study demonstrated the importance of humic substances for understanding transport and bioavailability of persistent organic pollutants. An understanding of metal binding sites in FA and HA proved essential to accurately model metal ion behavior in soil and water. In landscape-based studies, pesticides were preferentially bound to HA, reducing their mobility. Compost maturity and acceptability of other organic waste for land application were well evaluated by properties of HA extracted from these materials. A young humic fraction helped understand N cycling in paddy rice ( L.) soils, leading to improved rice management. The HA and FA fractions accurately represent natural organic matter across multiple environments, source materials, and research objectives. Studying them can help resolve important scientific and practical issues.

Polycyclic aromatic hydrocarbons (PAHs) and some biomarkers in the green sea turtles (Chelonia mydas)

Selected blood biochemical parameters (Glutathione S transferase: GST; Alanine aminotransferase: ALT; Aspartate aminotransferase: AST; Lactate dehydrogenase: LD and glucose) and polycyclic aromatic hydrocarbons (PAHs) were measured in blood samples from 18 green sea turtles (Chelonia mydas) from the Iranian coastline on the northern shore of the Sea of Oman. Mean total PAH concentration in the blood samples was 17.802 ± 1.006 ng/gdw. The study found no significant correlation between blood biochemical parameters and PAHs (p > 0.01), however significant correlations were found between total PAHs and GST activity (p < 0.01). The GST activity measured in this study was useful as a first investigation into the biological effects of PAH pollution as well as in determining the bioavailability of pollution. The results suggest that PAHs might be a factor influencing a reduction in green sea turtle egg fertilization and hatching success. Further study is needed concerning the effects of PAHs and other pollutants on green sea turtles, and specifically on the potential impact on the fetal development of green sea turtles.

Cadmium phytoextraction from contaminated paddy soil as influenced by EDTA and Si fertilizer.

The efficiency of heavy metal (HM) phytoextraction from contaminated soil directly depends on the pollutant bioavailability, which can be increased by some soil amendments. In field test, the impacts of soil-applied ethylenediaminetetraacetic acid (EDTA) and amorphous silicon dioxide (ASD) and foliar-applied monosilicic acid (MS) on cadmium (Cd) uptake by rice plants from contaminated paddy soil were investigated. Without EDTA, the solid or liquid Si materials reduced the Cd accumulation in the aboveground part of rice by 26 to 52%. If EDTA was applied, the Cd accumulation by plants was increased by 60 to 92%; however, the biomass was reduced by 16 to 35%. The combined application of Si-rich materials and EDTA provided enhanced plant tolerance to a negative influence of EDTA, while kept high Cd content in the rice stems and leaves. As a result, the Cd amounts extracted by the stems and leaves from the unit area of contaminated paddy soil were greater by 25 and 37% in comparison with those for only EDTA treatment.

Polycyclic aromatic hydrocarbons and potentially toxic elements in seafood from the Persian Gulf: presence, trophic transfer, and chronic intake risk assessment.

High bioavailability of man-made pollutants in marine environments raises serious concern regarding the safety of seafood. In the present study, the presence, trophic transfer, and risks of polycyclic aromatic hydrocarbons (PAHs), and potentially toxic elements (PTEs) in 170 benthic marine organisms (87 prawn; 28 crab; 55 fish) from the Persian Gulf were investigated. Among investigated species, E. coioides displayed the lowest level of metal pollution index (MPI), while P. armatus and P. semisulcatus showed the highest level of MPI and total PAHs, respectively. Principal component biplot exhibited a significant association of PTEs (except Hg) and PAHs in less motile benthic species. The results of trophic transfer investigation revealed that PTEs (except Hg) and PAHs were not biomagnified in the studied organisms through diet. However, Hg biomagnification factors greater than 1 indicated trophic transfer of mercury. In order to gain nutritional benefits of seafood, consumption of two fish/prawn meals/week for adults (except vulnerable groups such as pregnant women) and one fish/prawn meals/week for children is recommended. However, lifelong consumption of crabs (P. armatus) may threaten human health. In addition, the maximum allowable fish consumption rate (CRlim) for studied fish is 120g fish/day for adults and 30g fish/day for children. In the case of prawns, the safe dose is 30 and 10g prawns/day for adults and children, respectively.

Negligible effects of TiO2 nanoparticles at environmentally relevant concentrations on the translocation and accumulation of perfluorooctanoic acid and perfluorooctanesulfonate in hydroponically grown pumpkin seedlings (Cucurbita maxima × C. moschata)

Titanium dioxide nanoparticles (TiO2-NPs) are widely distributed in the environment. It has been demonstrated that TiO2-NPs could modify the environmental fate and bioavailability of organic pollutants, which affects ecological risks of TiO2-NPs and organic pollutants. In this study, the uptake, translocation and accumulation of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in pumpkin plants was investigated in the presence of TiO2-NPs. We reported for the first time the negligible effects of TiO2-NPs at environmentally relevant concentrations (0.05–5 mg/L) on the uptake and accumulation of PFOA and PFOS in hydroponically grown pumpkin seedlings regardless of root, stem and leaf. This phenomenon was independent of the initial concentrations of PFOA/PFOS and TiO2-NPs in the exposure solution. Also, seedling mass and contents of chlorophyll and anthocyanin were not affected by the co-exposure. Adsorption tests demonstrated the negligible adsorption of PFOA/PFOS on TiO2-NPs in the exposure solution. Moreover, uptake of PFOA/PFOS was insensitive to aquaporin inhibitor AgNO3 but significantly inhibited by niflumic acid (anion channel blocker) and 2,4-dinitrophenol (metabolic inhibitor) whereas Ti concentration in root was not affected by niflumic acid and 2,4-dinitrophenol but significantly decreased by AgNO3, indicating that transport of PFOA/PFOS and TiO2-NPs were via different routes into the pumpkin seedling. It was proposed that different pathways by which TiO2-NPs and PFOA/PFOS transported into the pumpkin seedling and negligible adsorption of PFOA/PFOS on TiO2-NPs contributed to the negligible effects of TiO2-NPs on the uptake, translocation and accumulation of PFOA/PFOS in pumpkin seedlings. In total, this work would improve our understanding of the ecological risks of TiO2-NPs in the environment.

Combination of chemical and toxicological methods to assess bioavailability of Tolclofos-methyl by earthworms

Tolclofos-methyl (TM) is an organophosphorus fungicide and widely utilized to control soil-borne diseases. However, toxic effects of TM on terrestrial invertebrates are still unknown. Here we measured the bioaccumulation of TM in earthworms (Eisenia fetida) to assess its environmental bioavailability. Mortality, weight change, and oxidative damage of earthworms were determined to investigate the toxicological bioavailability of TM. ROS, SOD and MDA in highest concentration treatment group significantly increased compared to the control group, suggesting that hazardous effects of TM to earthworms were caused by the oxidative stress. To further examine its toxicological bioavailability, cytotoxicity test was carried out by using extracted earthworm coelomocytes. The biomarkers, e.g., intracellular ROS, extracellular LDH, and cell viability showed correlation with TM in the culture media, demonstrating that cytotoxicity test could be employed to reflect the toxicological bioavailability of pollutants to earthworms or other organisms.

Bioavailability of microplastic-bound pollutants in vitro: The role of adsorbate lipophilicity and surfactants

The potential role of microplastic particles (MPs) as vectors for lipophilic organic pollutants enhancing their uptake by organisms has repeatedly been discussed in the scientific community. Likewise, several studies indicate an important role of surfactants in pollutant-transfer from MP to organisms. Employing polyethylene particles, the bioavailability of three MP-bound inducers of 7-ethoxyresorufin-O-deethylase (EROD) with variable lipophilicity was quantitatively compared via EROD activity in RTL-W1 cells. In addition, non-cytotoxic surfactant concentrations of Pluronic F-127, rhamnolipids, sodium deoxycholate and sodium dodecyl sulfate (SDS) supplemented to the medium were tested for their effects on pollutant desorption from MPs as well as on cellular EROD induction. Bioavailability of MP-bound pollutants was negatively correlated with lipophilicity, and all surfactants were found to modulate the cellular response towards inducers by unidentified mechanisms. After experimental correction for effects on the cellular response, all surfactants except SDS moderately increased desorption of inducer from MPs. Results on the impact of lipophilicity agree with previously published thermodynamic models, indicating that appreciable pollutant desorption from MPs may only occur for substances with comparatively low lipophilicity, the accumulation of which on MPs is negligible in the environment. However, the role of surfactants should be considered further with respect to potential effects on sorption of pollutants to and from MPs.

Environmental and Agricultural Relevance of Humic Fractions Extracted by Alkali from Soils and Natural Waters.

To study the structure and function of soil organic matter, soil scientists have performed alkali extractions for soil humic acid (HA) and fulvic acid (FA) fractions for more than 200 years. Over the last few decades aquatic scientists have used similar fractions of dissolved organic matter, extracted by resin adsorption followed by alkali desorption. Critics have claimed that alkali-extractable fractions are laboratory artifacts, hence unsuitable for studying natural organic matter structure and function in field conditions. In response, this review first addresses specific conceptual concerns about humic fractions. Then we discuss several case studies in which HA and FA were extracted from soils, waters, and organic materials to address meaningful problems across diverse research settings. Specifically, one case study demonstrated the importance of humic substances for understanding transport and bioavailability of persistent organic pollutants. An understanding of metal binding sites in FA and HA proved essential to accurately model metal ion behavior in soil and water. In landscape-based studies, pesticides were preferentially bound to HA, reducing their mobility. Compost maturity and acceptability of other organic waste for land application were well evaluated by properties of HA extracted from these materials. A young humic fraction helped understand N cycling in paddy rice ( L.) soils, leading to improved rice management. The HA and FA fractions accurately represent natural organic matter across multiple environments, source materials, and research objectives. Studying them can help resolve important scientific and practical issues.

Novel, Activated Carbon-Based Material for in-Situ Remediation of Contaminated Sediments.

Applying activated carbon (AC) to contaminated sediments is an in-situ approach to remediation with great potential. The bioavailability of persistent organic pollutants can be rapidly reduced and kept low over long periods of time. However, there are limitations to the method. The high buoyancy of AC particles makes their application difficult in the field, and AC retention on the amended site can be low in turbulent waters. Furthermore, the fine particles of powdered AC (PAC) can have adverse effects on organisms, but their remediation potential is superior to coarser, granular ACs (GAC). To tackle these shortcomings, a novel sorbent material was developed, consisting of PAC embedded into a stable, granular clay–matrix, significantly reducing buoyancy. These AC–clay granules (ACC-G) were tested for remediation potential (PCB-bioaccumulation reduction) and adverse effects on the benthic invertebrates Chironomus riparius and Lumbriculus variegatus. The novel ACC-G material was compared to GAC of the same particle size, the clay–matrix, and PAC. The findings show that ACC-G has a significantly higher remediation potential than GAC, allowing for reductions in PCB-bioaccumulation of up to 89%. Adverse effects could not be totally eliminated with ACC-G, but they were less severe than with PAC, likely due to the increased particle size.

Environmental quality survey of an industrialized estuary and an Atlantic Forest Biosphere Reserve through a comparative appraisal of organic pollutants

An evaluation of the concentrations, bioavailability and sources of polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants (POPs) was performed in the industrialized estuary of Santos-São Vicente and in the Cananéia-Iguape estuarine lagoon system, considered an Atlantic forest biosphere reserve, using different approaches. Semipermeable membrane devices (SPMDs) and bivalves (Crassostrea brasiliana) were deployed in both estuarine systems. Samples of water, suspended particulate material (PM), and sediments were also collected in these regions. The concentrations of PAHs in the water and in the PM from both estuarine systems were similar. In the sediment, the concentrations of PAHs and POPs were higher in the estuary of Santos-São Vicente than in the Cananéia-Iguape estuarine lagoon system. The accumulation of PAHs and POPs by the SPMD and C. brasiliana revealed that in both regions the bioavailability of contaminants was similar. Because of the hydrophobicity of the organic compounds, each matrix responded in a different manner to the source of the contaminants; C. brasiliana and sediment were primarily associated with 4–5 ring-PAHs that represent pyrolytic sources of hydrocarbons, whereas water and the SPMDs were correlated with the 2–3 ring-PAHs, which represent petrogenic sources. The PM produced an intermediated concentration among these compartments and was related to the concentration of POPs. Because no significant differences between the mean concentrations of contaminants in both studied regions were observed, anthropogenic effects currently impact the Cananéia-Iguape lagoon system, which was initially considered a pristine area.

Comparison of the accumulation and metabolite of fluoxetine in zebrafish larva under different environmental conditions with or without carbon nanotubes

Few studies have focused on the influence of environmental conditions on the bioavailability of pollutants interacted with nanomaterials in organisms. In this study, we primarily compared the influence of multiwalled carbon nanotubes (MWCNTs) on the bioavailability of fluoxetine in zebrafish (Danio rerio) larva under different environmental conditions: natural organic matter (NOM) and salinity. The results showed that fluoxetine accumulated in the larvae and then transformed into the metabolite norfluoxetine, with the metabolic rates from 2.8 to 3.5. Following co-exposure to MWCNTs, the accumulation of fluoxetine and norfluoxetine were further enhanced, suggesting a superior carrier of MWCNTs for fluoxetine, especially the functional MWCNTs. The consistent increase in the fluoxetine and norfluoxetine accumulation highlights the bioavailability of absorbed fluoxetine on MWCNTs in zebrafish larvae. The presence of NOM promoted the accumulation of fluoxetine and norfluoxetine in zebrafish, but alleviated the carrier effects of MWCNTs, acting as a natural antidote. Salinity negatively influenced the bioavailability of fluoxetine in the larvae, and further reversed the enhancements caused by MWCNTs. These findings provide a new insight into the influence of environmental conditions on the interactions between nanomaterials and pollutants in organisms.

Reducing plant uptake of a brominated contaminant (2,2′,4,4′‑tetrabrominated diphenyl ether) by incorporation of maize straw into horticultural soil

Application of crop residues is a conventional practice that contributes to crop production through nutrient returns and other benefits to soil health: driving soil physicochemical and biological functions. However, little is known about the impacts of straw residue incorporation on the bioavailability of organic pollutants and associated changes in microbial community structure in contaminated soils. In this study, maize straw was added to a soil contaminated with a model polybrominated diphenyl ether (BDE-47). A pot experiment was conducted and planted with carrot (Daucus carota L.). We found that straw addition greatly reduced the bioavailability of BDE-47, changed the bacterial community structure and affected a range of soil physiochemical properties. Moreover, the amount of BDE-47 that had accumulated in carrot roots and aboveground tissues was significantly reduced. This study may therefore describe an effective agronomic strategy to reduce the bioavailability of polybrominated diphenyl ethers (PBDEs) in a soil used to grow high value vegetable crops. This strategy draws on traditional wisdom and shows promise as a practical method to support horticultural production systems, remediate soils, and help to ensure food safety.

Signification of DNA integrity in sperm of Palaemon serratus (Pennant 1777): Kinetic responses and reproduction impairment

The study of the effects of contamination on sperm quality not only provides an early, specific and integrative response to the fraction of bioavailable pollutants, but also has been shown to predict the potential of this fraction to modify an organism's capacity to reproduce. In addition, fertility damage in invertebrates has been addressed as a major problem that may pose a threat to the maintenance of populations. In this context, the present study proposes a methodology based on the measurement of sperm DNA integrity to evaluate the impact of paternal damaged DNA on the reproductive success of Palaemon serratus. A preliminary methodological optimization step was carried out to assess the kinetics of response of spermatozoa as well as the sensitivity of the spermatozoa according to their location in the genital tract. Spermatozoa appeared to be sensitive to a short in vivo exposure to the direct acting agent methyl methanesulfonate (i.e. MMS; 2 days), with a persistence of damage even after a 30 days' recovery in a clean environment, suggesting a probable lack of DNA repair machinery. Moreover, our results revealed no difference in the level of DNA damage in mature spermatozoa whatever the exposure in spermatophore located in the terminal ampulla or in the proximal and distal part of the vas deferens. Finally, a significant decrease in the percentage of naturally bred prawns has been observed at the highest concentration of MMS (i.e. 100 μM). Nevertheless, no reproduction impairment (i.e. fertilization rate and early embryo development) following a paternal exposure has been shown in spite of very high levels of sperm DNA damage. In regard to the literature, this result raises questions concerning the kinetics of expression of genotoxic damage on progeny in the Palaemon model and future work will be led in this way.

Evaluation of pH-Dependent Metal Speciation Artifacts in Whole-Cell Bioreporter Analysis.

Whole-cell bacterial biosensors (bioreporters) are commonly applied for determination of metal toxicity and bioavailability in environmental samples. This is accomplished using a standard procedure whereby the sample is mixed with bioreporter cells suspended in a buffered medium at a fixed pH (set-point pH assay). This experimental approach can alter the sample pH. We therefore hypothesized that metal speciation artifacts compromising our ability to use bioreporters for determination of the "true" metal bioavailability in environmental samples may be introduced. Using the copper-specific bioreporter DF57-Cu15 as a model, we compared the conventional set-point pH assay to a flexible pH assay allowing for bioavailability determination at in situ sample pH. Our results demonstrate that pH-dependent metal speciation bias may occur when using the conventional set-point pH assay, and we recommend performing bioreporter measurements and calibrations at in situ sample pH. Although we only studied copper bioavailability, our results also have implications for bioreporter determination of other analytes displaying pH-dependent speciation such as other metals and some organics. We call for additional bioreporter studies of chemical speciation artifacts as this represents a problem hitherto overlooked in bioreporter literature. We thus conclude that there may be considerable scope for optimization of existing bioreporter assays for assessment of environmental pollutant bioavailability.