Trace elements fractionation in anaerobic digestates: Recommendation for using diffusive gradients in thin films passive samplers.

This study proposes an evaluation of the Diffusive Gradients in Thin films (DGT) technique to assess the labile fraction of trace metals and metalloids in anaerobic digestates. Experiments were performed in presence and absence of air to determine whether maintaining anaerobic conditions is mandatory during DGT deployments. A theoretically expected linear accumulation profile was observed for Fe, Mn, Ni, Mo, and As(III) in a manure-derived digestate and for Mn in distillery waste-derived digestate, whereas Al and Cu were detected without a consistent trend over time. The DGT technique can thus be used to evaluate the labile fraction of some trace elements in these digestates. The labile fraction of some elements was shown to evolve over 72 h when deployments were performed in the presence of air. We thus strongly recommend to systematically perform time-series deployments to identify and consider only the elements with a linear accumulation trend and to maintain anaerobic conditions.

Proposal of a new empirical model with flow velocity to improve time-weighted average concentration estimates from the Polar Organic Chemical Integrative Samplers.

It is now widely recognized that the sampling rate of Polar Organic Chemical Integrative Samplers (POCIS) is significantly affected by flow velocity, which can cause a consequent bias when determining time-weighted average concentrations (TWAC). We already observed the desorption of deisopropylatrazine (DIA) over time when added to the receiving phase of a POCIS. This desorption rate was particularly influenced by flow velocity, in an agitated water environment in situ. In the method presented here, we calibrated 30 pesticides under controlled laboratory conditions, varying the flow velocity over four levels. We simultaneously studied the desorption rate of DIA-d5 (a deuterated form of DIA) over time. An empirical model based on a power law involving flow velocity was used to process the information from the accumulation kinetics of the compounds of interest and elimination of DIA-d5. This type of model makes it possible to consider the effect of this crucial factor on exchange kinetics, and then to obtain more accurate TWACs with reduced bias and more acceptable dispersion of results.

Adaptation of the o-DGT for the sampling of 12 hormones: calibration, performance evaluation, and recommendation.

This work highlights the methodology for the development of diffusive gradients in thin films (o-DGT) through its adaptation for 12 natural and synthetic hormones belonging to three different families (estrogens, progestins, and androgens). A reliable strategy must be applied during o-DGT lab adaptation to avoid issues related to the analysis (i.e., presence of matrix effects in grab or passive samples) but also to the o-DGT configuration (i.e., undesirable sorption or desorption, lack of performance with insufficient elution or unreliable diffusion coefficient). To avoid analytical issues due to the presence of salts in grab samples, CaCl2 exposure solutions must be used on a lab-scale development to monitor the hormone concentration. The selected o-DGT was composed of an Oasis® HLB binding gel and a diffusive gel in agarose because they provided better performance than polyacrylamide gels (i.e., higher elution factors and more repeatable diffusion coefficients). The elution factors of the binding gel were then from 0.79 ± 0.13 to 1.04 ± 0.13 (RSD < 15%) and the diffusion coefficients at 25 °C were from 4.07 ± 0.24 to 5.49 ± 0.28 × 10-6 cm2 s-1 (RSD < 9%). A laboratory exposure to a synthetic solution was performed to check the consistency with the DGT quantification model validating the calibration parameters for all hormones (except 17α-ethinylestradiol with a bias of 40%). Therefore, the o-DGT configuration is suitable for sampling hormones in the natural environment with LOQDGT ranging from 0.3 to 6.6 ng L-1.

Interest of a new large diffusive gradients in thin films (L-DGT) for organic compounds monitoring: On-field comparison with conventional passive samplers.

In this work, the performances of a Large Diffusive Gradients in Thin films (L-DGT, i.e., a DGT based on a Chemcatcher® holder with a 5-fold larger sampling area) were compared on-field with the conventional DGT and the Polar Organic Chemical Integrative Sampler (POCIS) for the monitoring of a wide range of organic contaminants (i.e., 65 pesticides and metabolites, 53 pharmaceuticals and 12 hormones). These three passive samplers were simultaneously deployed in four rivers during 14 days. Their performances were then evaluated according to their detection and quantification capacities and their physical robustness. The results obtained confirm the advantages of the L-DGT over the conventional DGT regarding its sensitivity but also its robustness during field deployment. The POCIS provides the higher sensitivity, allowing the detection of more organic compounds compared to the DGT and, to a lesser extent, the L-DGT. However, both L-DGT and DGT reduces the uncertainty on the determination of the time-weighted average concentrations (CW), mainly due to the narrow range of variation of their calibration parameters. Indeed, for a given compound, CW can vary up to only a 3-fold factor with DGT and L-DGT compared to a 2 to 10-fold factor (up to 50) with POCIS. Thus, the L-DGT appears to be more suitable than DGT in low-contaminated contexts, which require higher sensitivity, or than POCIS when a CW determination is needed. For a qualitative evaluation however, the POCIS remains the most suitable passive sampler.

Multivariate Tiered Approach To Highlight the Link between Large-Scale Integrated Pesticide Concentrations from Polar Organic Chemical Integrative Samplers and Watershed Land Uses.

This paper presents a multi-step methodology to identify relationships between integrative pesticide quantifications and land uses on a given watershed of the Adour-Garonne Basin (Southwestern France). In fact, a large amount of pesticide concentration data was collected from 51 sites located in the Adour-Garonne Basin for a 1 year monitoring period in 2016. The sampling devices used here were polar organic chemical integrative samplers (POCIS), which provided time-weighted average concentration estimates. For each study site, its associated watershed and land cover distribution were determined using Corine Land Cover 2012 (CLC 2012) and Geographic Information System (GIS). The large-scale data were analyzed using multivariate statistical analyses, such as hierarchical cluster analysis (HCA) and principal component analysis (PCA). HCA grouped the 51 sites into five clusters with similar primary land uses. Next, the integrated pesticide concentration and land use distribution data sets were analyzed in a PCA. The key variables responsible for discriminating the sample sites showed distribution patterns consistent with specific land uses. To confirm these observations, pesticide fingerprints from sites with contrasting land uses were compared using a waffle method. The overall multivariate approach allowed for the identification of contamination sources related to their likely initial use, at the watershed level, that could be useful for preventing or containing pesticide pollution beyond simply acting on areas at risk.

Development of a multi-hormone analysis method by LC-MS/MS for environmental water application using diffusive gradient in thin films.

An analysis method for four families of hormones (estrogens, progestins, androgens and prostaglandins), dedicated to an efficient water monitoring with passive sampling, was developed using a liquid chromatography tandem mass spectrometry with triple quadrupole coupling and universal electrospray ionisation. Thirteen natural and synthetic hormones in ultra-pure water could be analysed in a single run according to the French Standard NF T90-210: calibration range of 0.1 (except for 17ß-Estradiol, Estriol, Estrone and Diethylstilbestrol, from 0.5 µg/L; and Ethinylestradiol, from 1 µg/L) to 20 µg/L with linear regressions (R2 ≥ 0.96), maximum accuracy deviations of 30% at intermediate fidelity for three concentration references (1, 10 and 20 µg/L) and instrumental LOQs from 0.05 to 1 µg/L. The stability of 11 hormones (10 µg/L) was studied under several storage conditions and sample evaporation. All selected hormones were stable for 60 days at -18 °C, 7 days at 4 °C and 7 days at 20 °C but continued drying flow after evaporation should be avoided, especially for 17α-Estradiol, Estrone and Diethylstilbestrol. Observed matrix effects using o-DGT extracts (diffusive gradient in thin-film sampler for polar organics) containing an environmental matrix varied from 24 to 92% but all matrix effects were corrected with IS use. Therefore, the developed method, coupled with o-DGT, was tested with the o-DGT deployment in rivers. Using diffusion coefficients from the literature or lab determined, the concentrations in the rivers varied for Estrone from 1.8 ng/L to 2.5 ng/L, and for Androstenedione from 0.4 to 1.1 ng/L.

Extraction of extracellular polymeric substances from dam lake fresh sediments derived from crystalline bedrock.

Extracellular polymeric substances (EPS) produced by microorganisms have a key role in the sedimentary compartment, e.g. promoting aggregation and biostabilisation of sediment particles and increasing chemical reactivity at the water/sediment interface. Therefore, proper extraction methods are needed to study this EPS matrix. In this work, nine extraction methods based on physical (centrifugation, sonication), chemical (sodium hydroxide, sodium pyrophosphate, sodium tetraborate), and both chemical and physical (cation exchange resins, i.e. CER) treatments and their combinations, as well as the solid:liquid ratio used for extraction, were compared based on the quantity and compositions of extracted EPS. The organic carbon extracted was quantified and the nature of biochemical macromolecules (proteins, polysaccharides, and humic-like compounds) was evaluated using colorimetric methods. The amount of ATP was used as an indicator of cell lysis and showed contamination with intracellular materials in EPS extracted with chemical methods. Moreover, chemical extraction presented a large quantity of impurities due to non-removal of reactant salts by ultracentrifugation. For the nine methods tested, humic-like substances represented the main fraction of the extracted EPS, but for chemical extraction, the presence of humic materials from the sediment organic fraction was due to non-specific extraction of the EPS fraction. Therefore, chemicals methods are not recommended to extract EPS from sediment. Despite their low extraction efficiency, physical methods and CER, i.e. 'soft' extraction methods, are preferred using a solid:liquid ratio 1:40.

Diffusive gradients in thin films (DGT): A suitable tool for metals/metalloids monitoring in continental waterbodies at the large network scale.

The contribution of Diffusive Gradients in Thin films (DGT) passive sampling to continental water quality monitoring was assessed in a real measurement network (6 sampling campaigns, 17 stations). Ten metals/metalloids (Al, Zn, Ni, Cd, Cu, Pb, Cr, As, Se and Sb) were studied using the control laboratory's working conditions with grab and DGT passive sampling. The DGT field deployments were robust, with a 3% sampler loss rate and a <65% average relative deviation between duplicates. Compared to grab sampling, DGT showed a similar quantification frequency for half of the targeted elements but showed a higher frequency for the other half (e.g., Cd quantification at 20% with grab sampling vs. 97% with DGT). Similar concentration trends were established using DGT and grab sampling at most sites throughout the year. Notably, for some elements, trends were only provided by DGT sampling. A study of several DGT blanks showed that the device contamination was occasional and originated primarily from cross-contamination during the disassembly step. Considering this contamination, the operational sensitivity by DGT was at least between 1 and 5 times greater in comparison to that by grab sampling. Estimations of the economic cost revealed that measurement networks cost 2 to 3 times more when monitored by DGT compared to standard grab monitoring. However, the information obtained based on each type of sampling method is different. Grab sampling is easy to implement and can highlight high contamination peaks. The DGT concentrations are averaged over time and are relevant to chronic exposure evaluations. Considering the good performance of the DGT sampling highlighted in this study and its complementarity with grab sampling in terms of water quality assessments, a combination of these two types of sampling, which can be affordable, should improve the water quality evaluation within monitoring networks.

Cadmium Selenide Formation Influences the Production and Characteristics of Extracellular Polymeric Substances of Anaerobic Granular Sludge.

Feeding cadmium (II) and selenium (IV) simultaneously to anaerobic granular sludge with the aim of synthesizing cadmium selenide (CdSe) nanoparticles induces compositional changes in the extracellular polymeric substances (EPS) matrix of this sludge. A methanogenic anaerobic granular sludge was repeatedly exposed to Cd(II) (10-50 mg L-1) and selenite (79 mg L-1) for 300 days at pH 7.3 and 30 °C in a fed-batch feeding regime for enrichment of Se-reducing bacteria and synthesis of CdSe nanoparticles. EPS fingerprints of the granular sludge, obtained by size exclusion chromatography coupled to a fluorescence detector, showed a significant increase in the intensity of protein-like substances with > 100 kDa apparent molecular weight (aMW) upon repeated exposure to Cd(II) and Se(VI). This was accompanied by a prominent decrease in protein-like substances of aMW < 10 kDa. The fingerprint of the humic-like substances showed emergence of a new peak with aMW of 13 to 300 kDa in the EPS extracted from the Cd/Se fed granular sludge. Experiments on metal(loid)-EPS interactions showed that the CdSe nanoparticles interact mainly with loosely bound EPS (LB-EPS). This study showed that the formation of Se(0) and CdSe nanoparticles occurs in the LB-EPS fraction of the granular sludge and repeated exposure to Cd and Se induces compositional changes in the EPS matrix.

Impact of low ionic strength on DGT sampling with standard APA gels: Effect of pH and analyte.

Only a limited and scattered knowledge is currently available on the conditions leading to the occurrence of sampling alteration at low ionic strength (<10-3 mol L-1) with DGT (diffusive gradients in thin films technique). In this study, the role of the pH and the charge of the analyte were comprehensively evaluated with DGT equipped with APA (polyacrylamide with agarose-derivative crosslinker) diffusive gels and ZrO or Chelex binding phases. The sampling of four cations (CdII, CuII, NiII and PbII) and two anions (AsV and CrVI) was compared for pH 4, 6 and 8 at common (10-2 mol L-1) and low (10-4 mol L-1) ionic strengths. Results showed that the sampling was modified at low ionic strength only in the most acidic condition (pH 4) for both anions and cations with an opposite incidence: cations' sampling was halved whereas anions' sampling was increased. Furthermore, cations sampling alteration was similarly reproduced using diffusion cell experiments, which requires only the APA gel, indicating that the binding layer does not participate in the low ionic strength effect. The intensity of DGT sampling modification was consistent with a prediction based on Donnan partitioning of analytes at gel/solution interface for several valences (from -I to + III). All these results strongly suggest that the APA diffusive gels carry positive charges that create a Donnan effect at low ionic strength. Since no ionic strength effect could be evidenced at pH 6 and 8, it can be reasonably assumed that this effect occurs only marginally for DGT deployments in most natural waters.

Adaptation of diffusive gradients in thin films technique to sample organic pollutants in the environment: An overview of o-DGT passive samplers.

The adaptation of the diffusive gradients in thin films technique (DGT) to sample organic pollutants in the environment, called o-DGT has been performed since 2011 for various types of organic compounds (e.g. pesticides, pharmaceuticals, hormones, endocrine disrupting chemicals, household and personal care products). To sample these different compounds, configuration of the samplers (mainly receiving phase and diffusive gel) has to be adapted. Up-to-date, sampling of 142 organic compounds by this passive sampler have been tested. This review provides the state-of-art of o-DGT passive sampler development, describing theory and modelling, calibration, configuration of the devices, and field applications. The most used configurations were agarose-XAD-18 and agarose-HLB configuration. o-DGT can be used to sample soils and most of natural waters (range of pH 4-9 and ionic strength 0.001-0.1 M). This review discusses current limitation of o-DGT in light of the feedback of DGT use to sample inorganic contaminants. It mainly concern the low sampling rates currently obtained by o-DGT compared to other passive samplers. This weakness could be compensated in the future with new sampler's design allowing an increase in exposure area.

A simultaneous assessment of organic matter and trace elements bio-accessibility in substrate and digestate from an anaerobic digestion plant.

This study evaluates a simultaneous assessment of organic matter (OM) and trace elements (TE) bio-accessibility in substrate and digestate from a full-scale anaerobic digester by a sequential OM extraction method. Simultaneous release of TE was determined along with the extraction of different OM fractions and the effects of extracting reagents on characteristics of OM were evaluated by nuclear magnetic resonance (NMR) spectroscopy. The reagents used for sequential extraction of OM were not enough selective. However, proteins were particularly removed by 0.1 M NaOH, while 72% H2SO4 mainly extracted hemicellulose and cellulose. The OM fractionation allowed for simultaneous extraction of >60% of total As, Cd, Co, Fe, Mn, Ni and Zn, while the extraction was limited for Al, Cr, Cu, Mo, and Pb. In substrate, >50% of total As, Co, Mn and Ni and <40% of total Fe, Zn and Mo were identified in bio-accessible fractions. In digestate, all elements demonstrated poor bio-accessibility except for As.

Evaluation of a mercapto-functionalized silica binding phase for the selective sampling of SeIV by Diffusive Gradients in Thin films.

This study evaluates binding discs based on 3-mercaptopropyl-functionalized silica gel for the selective sampling of selenite (SeIV) using Diffusive Gradients in Thin films sampler (DGT). SeIV accumulation was quantitative and selective over SeVI and followed the theoretical linear accumulation with the exposure time up to 0.7 µg. The sampling was not affected by ionic strength variations down to 10-2 mol L-1 (as NaNO3) but SeIV accumulation was found to decrease significantly for pH greater than 5 and was nearly zero at pH 9. Both the limited accumulation range and the pH dependence were unexpected because they have not been reported in the literature related to the SeIV trapping by thiol-based solid phases. Our experiments showed that after SeIV was bound to thiol functional groups, a further pH-dependent reaction occurred with free thiols, resulting in the reduction of SeIV into elemental selenium (Se0) followed by its release and back-diffusion through the DGT sampler. Unfortunately, such a reversible accumulation is incompatible with the implementation of the mercapto-functionalized silica binding phase in DGT devices for SeIV selective sampling.

Effect of digestate application on microbial respiration and bacterial communities' diversity during bioremediation of weathered petroleum hydrocarbons contaminated soils.

Digestate is an organic by-product of biogas production via anaerobic digestion processes and has a great potential as soil fertilizer due to concentrated nutrients. In this study, we examined digestate as a potential nutrient and microbial seeding for bioremediation of weathered (aged) petroleum hydrocarbon contaminated soils. We analysed 6 different treatments in microcosm using two industrial soils having different textures: a clay rich soil and a sandy soil. After 30 days of incubation, the highest total petroleum hydrocarbons (TPH) removal was observed in microcosms containing digestate together with bulking agent (17.8% and 12.7% higher than control in clay rich soil and sandy soil, respectively) or digestate together with immobilized bacteria (13.4% and 9% higher than control in clay rich soil and sandy soil, respectively). After digestate application microbial respiration was enhanced in sandy soil and inhibited in clay rich soil due to aggregates formation. After bulking agent addition to clay rich soil aggregates size was reduced and oxygen uptake was improved. Application of digestate to soil resulted in the development of distinct microbial groups in amended and non-amended soils. Genera containing species able to degrade TPH like Acinetobacter and Mycobacterium were abundant in digestate and in soil amended with digestate. Quantification of alkB genes, encoding alkane monoxygenase, revealed high concentration of these genes in digestate bacterial community. After application of digestate, the level of alkB genes significantly increased in soils and remained high until the end of the treatment. The study revealed great potential of digestate as a nutrient and bacteria source for soil bioremediation.

Distribution trend of trace elements in digestate exposed to air: Laboratory-scale investigations using DGT-based fractionation.

The use of digestate as amendment for agricultural soils has already been proposed as an alternative to mineral fertilizers or undigested organic matter. However, little information is available concerning the effect of digestate atmospheric exposure on trace elements speciation and, consequently, on their mobility and bio-accessibility when digestate is stored in open tanks or handled before land spreading. In this study, we investigated at laboratory-scale the effect of digestate aeration on the distribution of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se and W using the diffusive gradients in thin films technique (DGT)-based fractionation. For this purpose, experiments were performed to assess the variation in distribution between the labile, soluble and particulate fractions over time in digested sewage sludge during passive and forced aeration. Results showed that aeration promoted a dissolution of Al, As, Co, Cr, Cu, Fe, Mn, Mo and Pb, suggesting a possible increase in their mobility that may likely occur during storage in open tanks or handling before land spreading. Labile elements' fraction increased only during forced aeration (except for Fe and Mn), suggesting that their short-term bio-accessibility can increase only after significant aeration as the one assumed to occur when land spreading takes place.

Limitation of flow effect on passive sampling accuracy using POCIS with the PRC approach or o-DGT: A pilot-scale evaluation for pharmaceutical compounds.

Flow velocity is known to alter passive sampling accuracy. We investigated the POCIS (Polar Organic Chemical Integrative Sampler) with PRC (Performance Reference Compounds) approach and Diffusive Gradients in Thin Films samplers (o-DGT) to limit the effect of flow on the quantification accuracy of ten model pharmaceuticals compounds (0.16 ≤ log KOW ≤ 4.51). POCIS and o-DGT samplers were exposed for seven days in controlled pilot-scale (hundreds of liters) experiments under quiescent or flowing (2 < V < 18 cm s-1) conditions. Under flowing conditions, both POCIS-PRC and o-DGT efficiently limited the flow effect and led, in most cases, to biases within analytical uncertainty (20%). Under quiescent conditions, o-DGT performed accurately (bias < 30% for most compounds) whereas the PRC approach was unsuitable to improve upon the accuracy of POCIS (PRC was unable to desorb). Therefore, both approaches are helpful in limiting the effects of flow on accuracy, but only o-DGT is efficient in quiescent conditions. However, o-DGT currently suffers from poorer sensitivity compared to POCIS, but the future development of o-DGT devices with wider windows could overcome this limitation.

Combination of passive and grab sampling strategies improves the assessment of pesticide occurrence and contamination levels in a large-scale watershed.

Fifty-one monitoring stations from the Water Framework Directive network (2000/60/CE) were selected in the Adour-Garonne basin (117,650 km2, SW France). These stations were characterized by a diversity of land use, implying different water pesticide contamination profiles. In each, Polar Organic Chemical Integrative Sampler (POCIS) deployment (14 days) and grab water samples (1 per period) were performed 6 times in 2016 in order to obtain contamination levels (29 pesticides monitored). The large amount of data collected during this 1-year monitoring required specific graphical and map processing to compare the information provided by POCIS and grab samples. Graphical projections demonstrated that with POCIS the number of quantified pesticides and the quantification frequencies were higher than with grab samples. Additionally, projections showed that POCIS provided better temporal representativeness of monthly contamination levels. Indeed, the POCIS data showed seasonal trends which were directly linked with the use of each pesticide (application period) and the land use of each sampling site, that was not visible with the grab samples data. Map projections of the measured concentrations, using a common scale for the two sampling strategies, clearly showed the strengths of the POCIS deployment and the link between measured contamination levels, quantified pesticides and land use. Finally, this study shows that the combination of grab sample data (magnitude of contamination peaks) and POCIS data (average concentration over a given period) provided more complete and reliable knowledge of the contamination levels in the Basin than either method alone.

Assessment of the DGT technique in digestate to fraction twelve trace elements.

This study proposes an evaluation of the diffusive gradients in thin films technique (DGT) for studying trace elements in digested sewage sludge samples. Twelve elements were monitored by Chelex (Al, Cd, Co, Cr (III), Cu, Fe, Mn, Ni, Pb) and zirconia-DGT (As, Mo, Se) samplers exposed from 4 h to 9 days. Twenty-four hours' deployment time was suitable for most of the studied elements. However, short deployment led to insufficient element accumulation or non-establishment of steady state while long deployment (from 18 to 144 h depending on the element) led to saturation of the binding gels and/or competing effects with other major elements. In addition, this study showed that the matrix of the digested sewage sludge lowers the accumulation of some trace elements in the DGT samplers, leading to labile concentrations underestimation of roughly 10-30% (depending on the element). Moreover, compared to the conventional total dissolved elements measurement, DGT technique allowed to quantify 7 out of 12 labile elements whereas only 3 out of 12 dissolved elements were quantified. These results highlight the potential of DGT technique to assess labile trace elements in digestate samples, provided a careful adaptation of the deployment time as well as an evaluation of the matrix effect is performed.

Assessing arsenic redox state evolution in solution and solid phase during As(III) sorption onto chemically-treated sewage sludge digestate biochars.

This work aimed to determine the arsenic redox state distribution during As(III) sorption onto chemically-modified biochars. A solid-liquid extraction protocol using phosphoric (0.3 M) and ascorbic (0.5 M) acids at 80 °C for 20 min was established to ensure a quantitative recovery and stability of As(III) during the extraction. During sorption experiments, the redox conversions of As occurred and As(III) was either stable or partially oxidized in solution. The As distribution strongly varied depending on the biochar chemical treatment performed as well as the selected washing procedures (batch versus column washings). As(III) oxidation was favored with the KOH-modified biochar washed in batch mode. This oxidation was mostly induced by the biochar solid compounds rather than by soluble compounds released in solution. The As redox state distribution of As sorbed onto the biochars was successfully assessed using the extraction procedure. Arsenic was predominantly sorbed as As(III) (76-92%) onto the biochars.