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Wastewater-based epidemiology (WBE) has become a very useful tool to monitor a population's drug consumption or exposure to environmental and food contaminants. In this work, WBE has been applied to estimate tobacco consumption in seven Spanish regions. To this end, 24 h composite wastewater samples were taken daily for one week in 17 wastewater treatment plants, covering altogether a population of ca. 6 million inhabitants. The samples were treated by enzymatic deconjugation and the wastewater content of two human-specific nicotine metabolites (namely, cotinine and trans-3′-hydroxycotinine) was measured to estimate the daily consumption of nicotine. The population-weighted average nicotine consumption in the seven analyzed regions was 2.2 g/(day∙1000 inh.), without any daily pattern. This average estimated nicotine consumption value agreed with the value derived from official tobacco sales data. Differences in consumption among the seven studied regions were found, being Galicia, the region with the lowest rate, and the Basque Country and Catalonia those with the highest rates. However, no conclusive correlation was found between those values and the prevalence data taken from two different national surveys, nor sociodemographic and health data. This study demonstrates that this tool can complement other indicators in order to accurately assess tobacco consumption rates at regional and national levels and provides the most extensive application of the approach in the Spanish territory., Financial support This study was supported by MINECO/AEI projects (CTM2016-81935-REDT, CTM2017-84763-C3-2-R, CTM2017-84763-C3-1-R, CTM2017-84763-C3-3-R), MICINN project (CEX2018-000794-S), Galician Council of Culture, Education and Universities (ED481D 2017/003 and ED431C2017/36), cofunded by FEDER/ERDF.

The aim of this study was to ascertain the biocidal efficacy, based on the so-called C·t values, and the usage expenses of seven disinfection products in recreational waters using Escherich...

Soil pollution with trace elements is a concerning issue worldwide. Monitoring of soil pollution and remediation protocols need still from valid complementary analytical approaches able to detect changes in speciation and lability of metals in soils (e.g. stabilization or mobility). In this work, we compare three different analytical approaches to assess potential changes in environmental availability of Cu, As and Zn in a Mediterranean polluted soil that was amended with different combinations of iron sulphate and alkaline paper sludge waste. The studied methods were: (i) a standard large-bore flow-through column system (macrocolumn), (ii) an automatic dynamic flow-through microcolumn extraction system, and (iii) the diffusive gradients in thin gels technique (DGT). The three analytical approaches tested showed immobilization of Zn and Cu in contaminated mine soils after co-application of paper sludge and iron sulphate, but they differ quantitatively in terms of As mobility. Interconversion between oxidation states of inorganic As is observed to occur to a larger extent in macrocolumn. Because this may only occur in very specific Mediterranean scenarios (i.e. organic matter application to intermittently flooded mine soils), macrocolumn extraction procedures might not appropriately mimic the environmental availability of As in soils with organic amendments (e.g., paper sludge waste). Microcolumn leaching is the fastest screening tool to ascertain the efficiency of chemical amendments, but DGT is a good alternative with less technical demands.

Dynamic flow-through extraction is attracting a great deal of attention for real-time monitoring of the bioaccessible fraction of metal species in environmental solid substrates compared to its batchwise manual counterparts. There is however a lack of studies on the harmonization and validation of in vitro dynamic methods for physiologically based extraction tests against in vivo bioavailability methods. This work is aimed at evaluating the reliability of dynamic flow-through extraction methods for estimation of oral bioaccessible fractions of Cu, Zn, Pb, Ni, Cr, and As under worst-case extraction conditions in the gastric compartment based on the BGS102 guidance soil using the in vivo validated Unified BARGE (UBM) test, commonly performed under batchwise mode. Good overall agreement between batch and dynamic UBM results was obtained for the tested elements, except for Pb, as a consequence of the slow leaching kinetics identified with the dynamic method and the contribution of readsorption phenomena in the course of the gastric digestion. Metal-soil phase associations and their relationship with gastric bioaccessible fractions were elucidated using the so-called Chemometric Identification of Substrates and Element Distributions method based on sequential extraction with a variety of chemicals of increasing acidity as applied to both static and dynamic bioaccessibility data.

An automatic flow-through dynamic extraction method is proposed for the first time for in vitro exploration, with high temporal resolution, of the transit of the chyme from the gastric to the duodenal compartment using the Versantvoort's fed-state physiologically relevant extraction test. The flow manifold was coupled on-line to an inductively coupled plasma optical emission spectrometer (ICP OES) for real-time elucidation of the bioaccessible elemental fraction of micronutrients (viz., Cu, Fe and Mn) in food commodities across the gastrointestinal tract. The simulated intestinal and bile biofluid (added to the gastric phase) was successively pumped at 1.0 mL min−1 through a large-bore column (maintained at 37.0 ± 2.0 °C) initially loaded with a weighed amount of linseed (250 mg) using a PVDF filter membrane (5.0 μm pore size) for retaining of the solid sample and in-line filtration of the extracts. The lack of bias (trueness) of the on-line gastrointestinal extraction method coupled to ICP OES was confirmed using mass balance validation following microwave assisted digestion of the residual (non-bioaccessible) elemental fraction. Mass balance validation yielded absolute recoveries spanning from 79 to 121% for the overall analytes and samples. On-line dynamic extraction was critically appraised against batch counterparts for both gastric and gastrointestinal compartments. Due to the lack of consensus in the literature regarding the agitation method for batch oral bioaccessibility testing, several extraction approaches (viz., magnetic stirring, end-over-end rotation and orbital shaking) were evaluated. Improved gastric extractability of Fe along with bioaccessible data comparable to the dynamic counterpart based on the continuous displacement of the extraction equilibrium was obtained with batchwise magnetic stirring, which is deemed most appropriate for ascertaining worst-case/maximum bioaccessibility scenarios.

A novel biomimetic extraction procedure that allows for the in-line handing of ≥400 mg solid substrates is herein proposed for automatic ascertainment of trace element (TE) bioaccessibility in soils under worst-case conditions as per recommendations of ISO norms. A unified bioaccessibility/BARGE method (UBM)-like physiological-based extraction test is evaluated for the first time in a dynamic format for accurate assessment of in-vitro bioaccessibility of Cr, Cu, Ni, Pb and Zn in forest and residential-garden soils by on-line coupling of a hybrid flow set-up to inductively coupled plasma atomic emission spectrometry. Three biologically relevant operational extraction modes mimicking: (i) gastric juice extraction alone; (ii) saliva and gastric juice composite in unidirectional flow extraction format and (iii) saliva and gastric juice composite in a recirculation mode were thoroughly investigated. The extraction profiles of the three configurations using digestive fluids were proven to fit a first order reaction kinetic model for estimating the maximum TE bioaccessibility, that is, the actual worst-case scenario in human risk assessment protocols. A full factorial design, in which the sample amount (400-800 mg), the extractant flow rate (0.5-1.5 mL min(-1)) and the extraction temperature (27-37°C) were selected as variables for the multivariate optimization studies in order to obtain the maximum TE extractability. Two soils of varied physicochemical properties were analysed and no significant differences were found at the 0.05 significance level between the summation of leached concentrations of TE in gastric juice plus the residual fraction and the total concentration of the overall assayed metals determined by microwave digestion. These results showed the reliability and lack of bias (trueness) of the automatic biomimetic extraction approach using digestive juices.

In-line microdialysis is in this work hyphenated to electrothermal atomic absorption spectrometry via a dedicated flow-based interface for monitoring the batchwise leaching test endorsed by the Standards, Measurements and Testing Program (SMT) of the European Commission. The bioaccessible pool of lead in soils is measured using 0.43 mol/L AcOH as extractant. The proposed method allows to gain knowledge of leaching kinetics at real-time, simplify the overall procedure by accurate detection of steady-state conditions and overcome sample filtration or centrifugation. Soil leachates were automatically sampled at specified timeframes (e.g, every 20 or 80 min), processed in an external container (where dilution can be applied at will) and further injected into the atomizer. The method was experimentally validated by comparison of in situ microdialysis sampling results with in-line microfiltration in two soils of varying physicochemical properties. A mathematical framework was used for discrimination of different metal fractions (that is, readily mobilizable against slowly mobilizable lead) and also for estimating the total extractable lead under actual steady-state conditions. We have demonstrated that bioaccessibility tests lasting 16 h as endorsed by SMT might not suffice for ascertainment of maximum (steady-state) bioaccessibility of lead in terrestrial environments as demanded in risk assessment programs.

In situ automatic microdialysis sampling under batch-flow conditions is herein proposed for the first time for expedient assessment of the kinetics of lead bioaccessibility/bioavailability in contaminated and agricultural soils exploiting the harmonized physiologically based extraction test (UBM). Capitalized upon a concentric microdialysis probe immersed in synthetic gut fluids, the miniaturized flow system is harnessed for continuous monitoring of lead transfer across the permselective microdialysis membrane to mimic the diffusive transport of metal species through the epithelium of the stomach and of the small intestine. Besides, the addition of the UBM gastrointestinal fluid surrogates at a specified time frame is fully mechanized. Distinct microdialysis probe configurations and membranes types were investigated in detail to ensure passive sampling under steady-state dialytic conditions for lead. Using a 3-cm-long polysulfone membrane with averaged molecular weight cutoff of 30 kDa in a concentric probe and a perfusate flow rate of 2.0 μL min(-1), microdialysis relative recoveries in the gastric phase were close to 100%, thereby omitting the need for probe calibration. The automatic leaching method was validated in terms of bias in the analysis of four soils with different physicochemical properties and containing a wide range of lead content (16 ± 3 to 1216 ± 42 mg kg(-1)) using mass balance assessment as a quality control tool. No significant differences between the mass balance and the total lead concentration in the suite of analyzed soils were encountered (α = 0.05). Our finding that the extraction of soil-borne lead for merely one hour in the GI phase suffices for assessment of the bioavailable fraction as a result of the fast immobilization of lead species at near-neutral conditions would assist in providing risk assessment data from the UBM test on a short notice.

Accumulation of trace elements in diverse solid compartments and foodstuffs poses social concerns as to the adverse effects on the food webs and exposure risks to humans. This review surveys recent trends in the development of a new methodological approach for risk assessment, called flow-through dynamic extraction, for automatic bioaccessibility tests under worst-case conditions, and how it compares with consolidated batchwise, steady-state leaching methods. We critically describe and illustrate via representative examples novel analytical platforms to overcome the pressure drop in flow systems, the lack of sample representativeness and the sample throughput constraints with the aid of dedicated rugged liquid drivers and appropriate sample containers as a front end to atomic spectrometric detectors.

This paper reports the evaluation of in-vitro physiologically relevant extraction tests for ascertainment of the bioaccessible fractions of emerging flame retardants from indoor dust in the gastric and gastrointestinal compartments. Standardized bioaccessibility tests under both fasting (UBM-like test) and fed (FOREhST test) conditions simulating the macronutrient composition of an average child diet were harnessed for investigation of the oral bioaccessibility of chlorinated organophosphate esters, namely, tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCP), in household and automobile cabin dust samples with varying concentration levels of contaminants. Minimal processing of the biomimetic extracts (only protein precipitation using acetonitrile) was proven feasible by analysis with liquid chromatography-mass spectrometric detection (LC-MS/MS). An inversely proportional relationship was identified between log Kow and oral bioaccessibility concentrations for TCEP, TCPP and TDCP in both dust samples with maximum bioaccessibility fractions for TCEP within the range of 50–103%. Non-bioaccessible fractions were determined by matrix-solid phase dispersion. Limits of quantification of LC-MS/MS in surrogate digestive fluids ranging from 0.4–0.8 ng/mL suffice for determination of freely dissolved fractions of the two less hydrophobic species. Our results indicate that lipophilic food commodities used under fed-state gastrointestinal extraction conditions do not increase availability of TCEP, TCPP and TDCP in body fluids, and therefore conservative conditions in human health risk explorations for the target moderately polar flame retardants might be obtained with simplified tests under fasting conditions. This also holds true for the UBM/FOREhST bioaccessibility data for SRM 2585 (organic contaminants in house dust). Estimated average daily intake doses for toddlers incorporating oral bioaccessibility data afforded body burdens for the three chlorinated alkyl phosphates of ca. 3000 to 700 times below reference dose values, which indicate that long-term exposure to chlorinated organophosphate esters via accidental ingestion of indoor dust does not pose health risks to toddlers.

An automated dynamic leaching test integrated in a portable flow-based setup is herein proposed for reliable determination of readily bioaccessible Cr(VI) under worst-case scenarios in soils containing varying levels of contamination. The manifold is devised to accommodate bi-directional flow extraction followed by processing of extracts via either in-line clean-up/preconcentration using multi-walled carbon nanotubes or automatic dilution at will, along with Cr(VI) derivatization and flow-through spectrophotometric detection. The magnitude of readily mobilizable Cr(VI) pools was ascertained by resorting to water extraction as promulgated by current standard leaching tests. The role of carbon nanomaterials for the uptake of Cr(VI) in soil leachates and the configuration of the packed column integrated in the flow manifold were investigated in detail. The analytical performance of the proposed system for in vitro bioaccessibility tests was evaluated in chromium-enriched soils at environmentally relevant levels and in a standard reference soil material (SRM 2701) with a certified value of total hexavalent chromium. The automated method was proven to afford unbiased assessment of water-soluble Cr(VI) in soils as a result of the minimization of the chromium species transformation. By combination of the kinetic leaching profile and a first-order leaching model, the water-soluble Cr(VI) fraction in soils was determined in merely 6 h against >24 h taken in batchwise steady-state standard methods.

Dynamic flow-through extraction/fractionation methods have recently drawn much attention as appealing alternatives to the batchwise steady-state counterparts for the evaluation of environmentally available pools of potentially hazardous trace elements in solid matrices. The most critical weakness of flow-based column approaches lies in the small amount of solid that can be handled, whereby their applicability has been merely limited to date to the extraction of trace elements in highly homogeneous solid substrates; otherwise the representativeness of the test portion might not be assured. To tackle this limitation, we have devised an automated flow-through system incorporating a specially designed extraction column with a large volume capacity, wherein up to 2 g of solid sample could be handled without undue backpressure. The assembled flow setup was exploited for fast screening of potentially hazardous trace elements ( namely , Cd, Cr, Cu, Pb, and Zn) in highly inhomogeneous municipal solid waste incineration (MSWI) bottom ashes. The pools of readily mobilizable metal forms were ascertained using the Toxicity Characteristic Leaching Procedure (TCLP) based on the usage of 0.1 mol L −1 CH 3 COOH as leachant and analysis of extracts by inductively coupled optical emission spectrometry. The application of a two-level full factorial (screening) design revealed that the effect of sample fluidization primarily but other experimental factors such as the solid to liquid ratio and extractant flow rate significantly influenced the leachability of given elements in raw bottom ashes at the 0.05 significance level. The analytical performance of the novel flow-based method capitalized on fluidized-bed extraction was evaluated in terms of accuracy, through the use of mass balance validation, reproducibility and operational time as compared to batchwise extraction and earlier flow injection/sequential injection microcolum-based leaching tests.

There is a current worldwide interest for evaluating the potential reuse of municipal solid waste incineration (MSWI) bottom ash as a sub-base in road construction and secondary building material. Yet, there is a need for exploration of the physicochemical features of the bottom ashes to ensure environmental sustainability. To this end, batchwise water extraction as promulgated by the European norm EN 12457 or the German DIN 38414-S4 tests is commonly utilized to ascertain the impact of leachable trace elements in bottom ashes on biota. However, the above extraction protocols are not properly simulating the dynamic extraction conditions occurring in the nature, whereby the analytical information provided for risk assessment is debatable. In this work, a downscaled flow-through extraction method is proposed for mimicking the leaching of hazardous trace elements (namely, Pb, Zn, Cd, Cu and Cr) in MSWI bottom ashes by runoff waters more accurately than the manual counterparts. The flow assembly facilitates the full automation of standard and regulatory leaching tests by packing of a suitable amount of solid material into a column, whereupon the leaching reagent is continuously pumped through, thus yielding an accurate assessment of the environmentally significant water-extraction fraction with no effect from readsorption phenomena. The flow-through column system is exploited as a screening tool for fast evaluation of the influence of natural bottom ash weathering on the immobilization of hazardous elements to dictate the potential reuse of the solid waste. The dependence of sorption sites for humic substances on trace element leachability is also discussed. As compared to the steady-state approach, the dynamic method features the substantial shortening of the analytical extraction protocol from 24h to just 30min, better precision, with relative standard deviations (R.S.D.)11% versus20% R.S.D. for batchwise extraction, improved accuracy because of the absence of metal redistribution phenomena and minimization of manual operations as well as straightforward investigation of leaching rates for the suite of target elements.

An automatic in-vitro bioaccessibility test based upon dynamic microcolumn extraction in a programmable flow setup is herein proposed as a screening tool to evaluate bio-char based remediation of mine soils contaminated with trace elements as a compelling alternative to conventional phyto-availability tests. The feasibility of the proposed system was evaluated by extracting the readily bioaccessible pools of As, Pb and Zn in two contaminated mine soils before and after the addition of two biochars (9% (w:w)) of diverse source origin (pine and olive). Bioaccessible fractions under worst-case scenarios were measured using 0.001 mol L(-1) CaCl2 as extractant for mimicking plant uptake, and analysis of the extracts by inductively coupled optical emission spectrometry. The t-test of comparison of means revealed an efficient metal (mostly Pb and Zn) immobilization by the action of olive pruning-based biochar against the bare (control) soil at the 0.05 significance level. In-vitro flow-through bioaccessibility tests are compared for the first time with in-vivo phyto-toxicity assays in a microcosm soil study. By assessing seed germination and shoot elongation of Lolium perenne in contaminated soils with and without biochar amendments the dynamic flow-based bioaccessibility data proved to be in good agreement with the phyto-availability tests. Experimental results indicate that the dynamic extraction method is a viable and economical in-vitro tool in risk assessment explorations to evaluate the feasibility of a given biochar amendment for revegetation and remediation of metal contaminated soils in a mere 10 min against 4 days in case of phyto-toxicity assays.