Oral bioaccessibility of PTEs in soils: A review of data, influencing factors and application in human health risk assessment.

Understanding the behavior of metal(loi)ds transported from soil to humans is critical for human health risk assessment (HHRA). In the last two decades, extensive studies have been conducted to better assess human exposure to potentially toxic elements (PTEs) by estimating their oral bioaccessibility (BAc) and quantifying the influence of different factors. This study reviews the common in vitro methods used to determine the BAc of PTEs (in particular As, Cd, Cr, Ni, Pb, and Sb) under specific conditions (particularly in terms of the particle size fraction and validation status against an in vivo model). The results were compiled from soils derived from various sources and allowed the identification of the most important influencing factors of BAc (using single and multiple regression analyses), including physicochemical soil properties and the speciation of the PTEs in question. This review presents current knowledge on integrating relative bioavailability (RBA) in calculating doses from soil ingestion in the HHRA process. Depending on the jurisdiction, validated or non-validated bioaccessibility methods were used, and risks assessors applied different approaches: (i) using default assumptions (i.e., RBA of 1); (ii) considering that bioaccessibility value (BAc) accurately represents RBA (i.e., RBA equal to BAc); (iii) using regression models to convert BAc of As and Pb into RBA as proposed by the USA with the US EPA Method 1340; or (iv) applying an adjustment factor as proposed by the Netherlands and France to use BAc from UBM (Unified Barge Method) protocol. The findings from this review should help inform risk stakeholders about the uncertainties surrounding using bioaccessibility data and provide recommendations for better interpreting the results and using bioaccessibility in risk studies.

Field evaluation of industrial non-food crops for phytomanaging a metal-contaminated dredged sediment.

Phytomanagement is a concept fit for a bio-based circular economy that combines phytotechnologies and biomass production for non-food purposes. Here, ten annual and perennial industrial non-food crops (Sorghum Biomass 133, Sorghum Santa Fe red, Linum usitatissimum L., Eucalyptus sp., Salix Inger, Salix Tordis, Beta vulgaris L., Phacelia tanacetifolia Benth., Malva sylvestris L., and Chenopodium album L.) were studied under field conditions for phytomanaging a metal (Cd, Cu, Pb, and Zn)-contaminated dredged sediment in the North of France. The crops were selected according to their relevance to pedoclimatic and future climatic conditions, and one or more non-food end-products were proposed for each plant part collected, such as biogas, bioethanol, compost, natural dye, ecocatalyst, and fiber. Based on the soil-plant transfer of metals, eight out of the crops cultivated on field plots exhibited an excluder behavior (bioconcentration factor, BCF < 1), a trait suitable for phytostabilization. However, these crops did not change the metal mobilities in the dredged sediment. The BCF < 1 was not sufficient to characterize the excluder behavior of crops as this factor depended on the total dredged-sediment contaminant. Therefore, a BCF group ranking method was proposed accounting for metal phytotoxicity levels or yield decrease as a complemental way to discuss the crop behavior. The feasibility of the biomass-processing chains was discussed based on these results and according to a survey of available legislation in standard and scientific literature.

Phytoextraction of Zn and Cd with Arabidopsis halleri: a focus on fertilization and biological amendment as a means of increasing biomass and Cd and Zn concentrations.

The current work aims to investigate the influence of fertilization (fertilizer) and fungal inoculation (Funneliformis mosseae and Serendipita indica (formerly Piriformospora indica), respectively arbuscular mycorrhizal (AMF) and endophytic fungi) on the phytoextraction potential of Arabidopsis halleri (L.) O'Kane & Al-Shehbaz (biomass yield and/or aboveground part Zn and Cd concentrations) over one life plant cycle. The mycorrhizal rates of A. halleri were measured in situ while the fungal inoculation experiments were carried out under controlled conditions. For the first time, it is demonstrated that the fertilizer used on A. halleri increased its biomass not only at the rosette stage but also at the flowering and fruiting stages. Fertilizer reduced the Zn concentration variability between developmental stages and increased the Cd concentration at fruiting stage. A. halleri roots did not show AMF colonization at any stage in our field conditions, neither in the absence nor in the presence of fertilizer, thus suggesting that A. halleri is not naturally mycorrhizal. Induced mycorrhization agreed with this result. However, S. indica has been shown to successfully colonize A. halleri roots under controlled conditions. This study confirms the benefit of using fertilizer to increase the phytoextraction potential of A. halleri. Overall, these results contribute to the future applicability of A. halleri in a phytomanagement strategy by giving information on its cultural itinerary.

Phytomanagement of a metal(loid)-contaminated agricultural site using aromatic and medicinal plants to produce essential oils: analysis of the metal(loid) fate in the value chain.

Phytomanagement uses plants and soil conditioners to create value on contaminated land while minimizing environmental risk. This work was carried out on a metal(loid)-contaminated site and aimed at assessing the suitability of Salvia sclarea L. (sage) and Coriandrum sativum L. (coriander) combined with an arbuscular mycorrhizal fungus (AMF) inoculant to immobilize metal(loid)s and produce essential oils (EO). The effect of the inoculant on the transfer of metal(loid)s (ML, i.e., Cd, Cu, Pb, Zn, As, Ni, and Sb) to plants and the ML soil mobility were investigated. The ML concentrations in EO from both plant species and the valorization options for the distillation residues (soil conditioner, animal fodder, and anaerobic digestion) were studied. Sage was a suitable candidate for this value chain because it presents an excluder phenotype and the residues of oil extraction could be used as a soil conditioner. The metal concentrations in the sage EO were similar to those obtained from plants cultivated on an uncontaminated soil. These results indicate the suitability of sage harvested on the contaminated soil according to the ML fate in the whole value chain. Like the EO of sage, ML concentrations in the coriander EO did not differ from those in the commercial EO that were obtained from plants grown on uncontaminated soil. However, the use of distillation residues of coriander was limited by their relatively elevated Cd concentrations. The use of a mycorrhizal inoculum did not decrease the Cd mobility in soil for the coriander.

Accurate analysis of HCl in biomethane using laser absorption spectroscopy and ion-exchange chromatography.

Biomethane is a renewable energy gas with great potential to contribute to the diversification and greening of the natural gas supply. Ideally, biomethane can directly be injected into the natural gas grid system. For grid injection, specifications such as those in EN 16723-1 shall be met. One of the impurities to be monitored is hydrogen chloride (HCl). To assess conformity with the specification for HCl, accurate and reliable test methods are required. Here, we report the development of three novel test methods, based on a variety of laser absorption spectroscopy techniques (Direct absorption spectroscopy-DAS and wavelength modulation spectroscopy-WMS) and ion-exchange chromatography, for the measurement of HCl in biomethane. Gas mixtures of HCl in biomethane were used to demonstrate the performance of the spectroscopic systems in the nmol mol-1 to low µmol mol-1 ranges, achieving uncertainties in the 4% range, k = 2. For ion-exchange chromatography analysis, HCl was first collected on an alkali-impregnated quartz fiber filter. The analysis was performed according to ISO 21438-2 and validated using synthetic biomethane spiked with HCl. The relative expanded uncertainties for the ion exchange chromatography HCl measurements are in the 10-37% range, k = 2. The results presented for the 3 test methods demonstrate that the respective methods can be used for HCl conformity assessment in biomethane.

Establishing guidelines to harmonize tumor mutational burden (TMB): in silico assessment of variation in TMB quantification across diagnostic platforms: phase I of the Friends of Cancer Research TMB Harmonization Project.

BACKGROUND: Tumor mutational burden (TMB), defined as the number of somatic mutations per megabase of interrogated genomic sequence, demonstrates predictive biomarker potential for the identification of patients with cancer most likely to respond to immune checkpoint inhibitors. TMB is optimally calculated by whole exome sequencing (WES), but next-generation sequencing targeted panels provide TMB estimates in a time-effective and cost-effective manner. However, differences in panel size and gene coverage, in addition to the underlying bioinformatics pipelines, are known drivers of variability in TMB estimates across laboratories. By directly comparing panel-based TMB estimates from participating laboratories, this study aims to characterize the theoretical variability of panel-based TMB estimates, and provides guidelines on TMB reporting, analytic validation requirements and reference standard alignment in order to maintain consistency of TMB estimation across platforms. METHODS: Eleven laboratories used WES data from The Cancer Genome Atlas Multi-Center Mutation calling in Multiple Cancers (MC3) samples and calculated TMB from the subset of the exome restricted to the genes covered by their targeted panel using their own bioinformatics pipeline (panel TMB). A reference TMB value was calculated from the entire exome using a uniform bioinformatics pipeline all members agreed on (WES TMB). Linear regression analyses were performed to investigate the relationship between WES and panel TMB for all 32 cancer types combined and separately. Variability in panel TMB values at various WES TMB values was also quantified using 95% prediction limits. RESULTS: Study results demonstrated that variability within and between panel TMB values increases as the WES TMB values increase. For each panel, prediction limits based on linear regression analyses that modeled panel TMB as a function of WES TMB were calculated and found to approximately capture the intended 95% of observed panel TMB values. Certain cancer types, such as uterine, bladder and colon cancers exhibited greater variability in panel TMB values, compared with lung and head and neck cancers. CONCLUSIONS: Increasing uptake of TMB as a predictive biomarker in the clinic creates an urgent need to bring stakeholders together to agree on the harmonization of key aspects of panel-based TMB estimation, such as the standardization of TMB reporting, standardization of analytical validation studies and the alignment of panel-based TMB values with a reference standard. These harmonization efforts should improve consistency and reliability of panel TMB estimates and aid in clinical decision-making.

Urban soil phytomanagement for Zn and Cd in situ removal, greening, and Zn-rich biomass production taking care of snail exposure.

The phytoextraction potential of Arabidopsis halleri (L.) O'Kane & Al Shehbaz and Salix viminalis L. to partially remove Zn and Cd in soil was investigated. In an urban field site, a very short rotation coppice of willows was implemented, and growth parameters were monitored for 3 years. A. halleri was cultivated in the same site with or without fertilizer to improve biomass yield and/or Zn and Cd aerial part concentrations. Effects of harvest and co-cultivation on these two parameters were measured. To determine if willows and A. halleri leaves were risky in case of consumption by a herbivorous invertebrate like the landsnail Cantareus aspersus, metal concentrations of snails fed with Zn- and Cd-enriched and low enriched leaves were compared. Willows and A. halleri grew well on the metal-contaminated soil (1.7 and 616 mg kg-1 Cd and Zn, respectively). The A. halleri Zn foliar concentration reached the Zn hyperaccumulation threshold (> 10,000 mg kg-1 DW) in the presence of NPK fertilizer and although the soil was alkaline (pH > 8.2). Cd concentration increased with harvest and fertilizer. Cd and Zn foliar concentrations of willows were far above baseline values. Laboratory snails exposure revealed that willow leaves ingestion caused a moderate increase of Cd, Pb, and Zn bioaccumulation in snails compared to the one caused by A. halleri ingestion. The soil and plant metal concentrations were reflected by field snail biomonitoring. This study confirmed the interest of selecting A. halleri and willows to partially remove Zn and Cd in the soil and emphasized their potential usefulness in greening urban contaminated area and producing raw materials for green chemistry while paying attention to the environmental pollutant transfer.

Method development and inter-laboratory comparison about the determination of titanium from titanium dioxide nanoparticles in tissues by inductively coupled plasma mass spectrometry.

Nanosized titanium dioxide (TiO2) is one of the most interesting and valuable nanomaterials for the construction industry but also in health care applications, food, and consumer goods, e.g., cosmetics. Therefore, the properties associated with this material are described in detail. Despite its widespread use, the analytical determination and characterization of nanosized metal oxides is not as straightforward as the comparatively easy-to-detect metallic nanoparticles (e.g., silver or gold). This study presents the method development and the results of the determination of tissue titanium (Ti) levels after treatment of rats with the nanosized TiO2. Total Ti levels were chosen to evaluate the presence and distribution of TiO2 nanoparticles. A procedure consisting of incubation with a mixture of nitric acid (HNO3) and hydrofluoric acid (HF), and heating was developed to digest tissues and TiO2 nanomaterials in order to determine the total Ti content by inductively coupled plasma mass spectrometry (ICPMS). For the inter-laboratory comparison, altogether four laboratories analyzed the same samples upon digestion using the available ICPMS equipment. A major premise for any toxicokinetic study is the possibility to detect the chemical under investigation in biological samples (tissues). So, the study has to be performed with a dose high enough to allow for subsequent tissue level measurement of the chemical under investigation. On the other hand, dose of the chemical applied should not induce over toxicity in the animal as this may affect its absorption, distribution, metabolism, and excretion. To determine a non-toxic TiO2 dosage, an acute toxicity study in rats was performed, and the organs obtained were evaluated for the presence of Ti by ICPMS. Despite the differences in methodology and independent of the sample preparation and the ICPMS equipment used, the results obtained for samples with Ti concentrations >4 µg Ti/g tissue agreed well.

The evaluation of an analytical protocol for the determination of substances in waste for hazard classification.

The classification of waste as hazardous could soon be assessed in Europe using largely the hazard properties of its constituents, according to the the Classification, Labelling and Packaging (CLP) regulation. Comprehensive knowledge of the component constituents of a given waste will therefore be necessary. An analytical protocol for determining waste composition is proposed, which includes using inductively coupled plasma (ICP) screening methods to identify major elements and gas chromatography/mass spectrometry (GC-MS) screening techniques to measure organic compounds. The method includes a gross or indicator measure of 'pools' of higher molecular weight organic substances that are taken to be less bioactive and less hazardous, and of unresolved 'mass' during the chromatography of volatile and semi-volatile compounds. The concentration of some elements and specific compounds that are linked to specific hazard properties and are subject to specific regulation (examples include: heavy metals, chromium(VI), cyanides, organo-halogens, and PCBs) are determined by classical quantitative analysis. To check the consistency of the analysis, the sum of the concentrations (including unresolved 'pools') should give a mass balance between 90% and 110%. Thirty-two laboratory samples comprising different industrial wastes (liquids and solids) were tested by two routine service laboratories, to give circa 7000 parameter results. Despite discrepancies in some parameters, a satisfactory sum of estimated or measured concentrations (analytical balance) of 90% was reached for 20 samples (63% of the overall total) during this first test exercise, with identified reasons for most of the unsatisfactory results. Regular use of this protocol (which is now included in the French legislation) has enabled service laboratories to reach a 90% mass balance for nearly all the solid samples tested, and most of liquid samples (difficulties were caused in some samples from polymers in solution and vegetable oil). The protocol is submitted to French and European normalization bodies (AFNOR and CEN) and further improvements are awaited.