Uptake of perfluorinated alkyl acids by crops: results from a field study.

Four crops with different edible plant parts (radish, lettuce, pea and maize) were grown in outdoor lysimeters on soil spiked with 13 perfluorinated alkyl acids (PFAAs) at 4 different levels. PFAA concentrations were measured in soil, soil pore water, and different plant parts at harvest. Edible part/soil concentration factors ranged over seven orders of magnitude and decreased strongly with increasing PFAA chain length, by a factor of 10 for each additional fluorinated carbon (nCF) for pea. Three processes were responsible for most of the variability. The first was sorption to soil; calculating whole plant concentration factors on the basis of concentration in pore water instead of soil reduced the variability from five orders of magnitude to two. Second, the journey of the PFAAs with the transpiration stream to the leaves was hindered by retention in the roots driven by sorption; root retention factors increased by a factor 1.7 for each nCF. Third, transfer of PFAAs from the leaves to the fruit via the phloem flow was also hindered - presumably by sorption; fruit/leaf concentration factors decreased by a factor 2.5 for each nCF. A simple mathematical model based on the above principles described the measured concentrations in roots, leaves, fruits and radish bulbs within a factor 4 in most cases. This indicates that the great diversity in PFAA transfer from soil to crops can be largely described with simple concepts for four markedly different species.

Conserved C-terminal motifs in odorant receptors instruct their cell surface expression and cAMP signaling.

The highly individual plasma membrane expression and cAMP signaling of odorant receptors have hampered their ligand assignment and functional characterization in test cell systems. Chaperones have been identified to support the cell surface expression of only a portion of odorant receptors, with mechanisms remaining unclear. The presence of amino acid motifs that might be responsible for odorant receptors' individual intracellular retention or cell surface expression, and thus, for cAMP signaling, is under debate: so far, no such protein motifs have been suggested. Here, we demonstrate the existence of highly conserved C-terminal amino acid motifs, which discriminate at least between class-I and class-II odorant receptors, with their numbers of motifs increasing during evolution, by comparing C-terminal protein sequences from 4808 receptors across eight species. Truncation experiments and mutation analysis of C-terminal motifs, largely overlapping with helix 8, revealed single amino acids and their combinations to have differential impact on the cell surface expression and on stimulus-dependent cAMP signaling of odorant receptors in NxG 108CC15 cells. Our results demonstrate class-specific and individual C-terminal motif equipment of odorant receptors, which instruct their functional expression in a test cell system, and in situ may regulate their individual cell surface expression and intracellular cAMP signaling.

Transfer of Per- and Polyfluoroalkyl Substances (PFAS) from Feed into the Eggs of Laying Hens. Part 2: Toxicokinetic Results Including the Role of Precursors.

A feeding study was performed to examine the bioaccumulation of per- and polyfluoroalkyl substances (PFAS) in laying hens' tissues and plasma and feed-to-egg transfer rates and half-lives. A 25 day exposure was followed by a 42 day depuration period. A target analysis revealed substantial amounts of the precursors N-methyl and N-ethyl perfluorooctane sulfonamidoacetic acid (Me- and EtFOSAA), perfluorooctane sulfonamidoacetic acid (FOSAA), and perfluorooctane sulfonamide (FOSA). In tissues and eggs, the highest bioaccumulation was found for PFHxS, PFHpS, PFOS, and PFOA. Low levels of PFHxS (all samples), PFOS, and FOSAA (in yolk) were measurable even after the depuration period. The egg elimination half-lives of PFOS and aforementioned precursors were estimated to be 4.3 days, while the transfer rates of PFOS and all precursors taken together were 0.99. The transfer rate of PFOA was around 0.49. PFHxS and PFHpS showed apparent transfer rates of >100%, which is hypothesized to indicate the presence of precursors.

Transfer of Per- and Polyfluoroalkyl Substances (PFAS) from Feed into the Eggs of Laying Hens. Part 1: Analytical Results Including a Modified Total Oxidizable Precursor Assay.

The group of per- and polyfluoroalkyl substances (PFAS) comprises thousands of chemicals, which are used in various industrial applications and consumer products. In this study, a feeding experiment with laying hens and feed grown on a contamination site was conducted, and PFAS were analyzed in the feed and eggs to assess the transfer of PFAS into eggs. A targeted analysis of perfluoroalkyl acids (PFAAs) and different sulfonamides was performed. Additionally, the total oxidizable precursor (TOP) assay was modified by fully oxidizing small amounts of the samples instead of oxidizing their extracts in order to overcome potential losses during extraction. Targeted analysis showed the presence of known PFAAs and four sulfonamides in the feed and egg yolk samples. In the plant-based feed, short-chain PFAAs, methyl and ethyl perfluorooctane sulfonamidoacetic acid (Me- and EtFOSAA), and perfluorooctane sulfonic acid (PFOS) were the most abundant PFAS. In the eggs, PFOS, FOSAA, and its alkylated homologues showed the highest concentrations. The TOP assay revealed the presence of substantial amounts of precursors with different chain lengths from C4 to C8. The highest relative increase of PFOA after oxidation was observed in egg yolk from the end of the exposure period (828%). The results of this study demonstrate the transfer of PFAAs and their precursors into hens' eggs and emphasize the contribution of (known and unidentified) precursors to the overall PFAS burden in edible products. The modified TOP assay approach was shown to be a powerful tool to better assess the total burden of samples with PFAS.

Influence of soil on the uptake of perfluoroalkyl acids by lettuce: A comparison between a hydroponic study and a field study.

This study explores whether mechanistic understanding of plant uptake of perfluoroalkyl acids (PFAAs) derived from hydroponic experiments can be applied to soil systems. Lettuces (Lactuca sativa) were grown in outdoor lysimeters in soil spiked with 4 different concentrations of 13 PFAAs. PFAA concentrations were measured in soil, soil pore water, lettuce roots, and foliage. The PFAA uptake by the lettuce was compared with uptake measured in a hydroponic study. The foliage:pore water concentration ratios in the lysimeter were similar to the foliage:water concentration ratios from the hydroponic experiment. In contrast, the root:pore water concentration ratios in the lysimeter were 1-2 orders of magnitude lower than in the hydroponic study for PFAAs with 6 or more perfluorinated carbons. Hence, hydroponic studies can be expected to provide a good quantitative measure of PFAA transfer from soil to foliage if one accounts for soil:pore water partitioning and differences in transpiration rate. However, hydroponic studies will be of little value for estimating PFAA transfer from soil to roots because sorption to the root surface is greatly enhanced under hydroponic conditions.

Per- and polyfluoroalkyl substances in the German environment - Levels and patterns in different matrices.

Per- and polyfluoroalkyl substances (PFAS) in the environment mostly originate from emissions of previously unregulated PFAS. However, there are also many documented incidents of accidental releases. To track such releases, it is essential to distinguish between typical background contamination and legally relevant incidents. This requires a comprehensive overview of all PFAS present in the environment, which is currently only possible to a limited extent due to the large variety of individual compounds. In the present study, a multimethod for capturing 41 PFAS including perfluoroalkyl acid (PFAA) precursors is introduced. The applicability of the method was tested on terrestrial, freshwater and marine samples from the German Environmental Specimen Bank (ESB), thereby providing a rough overview of PFAS contamination in German environment. Special focus was put on soil samples from ESB sites across Germany in comparison to soil samples from a polluted site in south-west Germany. The method was successfully applied to environmental samples. In total, 31 PFAS were detected, among them PFAA precursors and fluorinated ethers. Substance patterns differed between sites and matrices. In ESB soil samples from 2014 (n = 11), the sum of all captured PFAS ranged between 0.75 and 19.5 µg kg-1 dry weight (dw), while concentrations between 416 µg kg-1 and 3530 µg kg-1 were detected in samples from the incident site (n = 10). In other matrices, total PFAS concentrations were magnitudes lower. Highest concentrations were observed for PFOS in bream livers from the Saale (226 µg kg-1). Given the heterogeneous patterns, it will require further broadly-based monitoring data to allow for a solid estimation of relevant background levels. The data provided here may support the differentiation between background levels and hotspot contaminations.

Fate of Chlorpropham during High-Temperature Processing of Potatoes.

Chlorpropham is a widely used sprouting inhibitor applied on potatoes during their storage. Currently, severe concerns are raised regarding the potential formation of 3-chloroaniline from chlorpropham during heat treatment. The reactions degrading the molecule in the matrix are quite complex under harsh processing conditions, and a molecular investigation is thus challenging. This study aims to decipher the reaction pathways and to discover new metabolites in typical high-temperature food-processing steps. For this purpose, potatoes were treated with 14C-radiolabeled chlorpropham, stored for up to 6 months, and subjected to the traditional preparation steps of boiling, frying, and baking. A quantification method including an acidic hydrolysis was developed for analysis of free and bound analytes. All conducted processing steps led to a substantial mitigation of chlorpropham residues in the consumable products. Of the residues, 17 ± 6% remained in boiled tubers, while 27 ± 3 and 22 ± 3% remained in the fried and baked products, respectively. Chlorpropham was transferred into the surrounding media (boiling water, frying oil, and air, respectively). 3-Chloroaniline was only (raw tubers) or predominantly (processed tubers) present as a bound analyte and was shown to form during storage but not during processing. Additionally, nonextractable and nonquantified residues were detected in the baked and in the long-term-stored tubers after processing. Future studies will have to balance beneficial (mitigating) and potentially hazardous aspects of these results. By transferring the 14C-food-processing approach to a variety of substances, ingredients, and processes, it will be possible to further understand chemical reactions in food processing, finally leading to safer food.

Processing Induced Degradation Routes of Prochloraz in Rapeseed Oil.

Analyzing the fate of substances in complex matrices, such as processed food, is a major challenge in modern analytical chemistry. However, current regulatory procedures for pesticides only include high temperature hydrolysis of the active substance in water (OECD 507) to simulate food processing. This study shows that heating radiolabeled [imidazolyl-2-14C]prochloraz in virgin rapeseed oil at temperatures up to 240 °C leads to an extensive degradation of the active substance. In total, 11 degradation products were identified. Several of these products were formed by reactions of the active substance with ingredients from the oil. 2-[(1-H-Imidazole-1-carbonyl)(propyl)amino]ethyl oleate (icpame-oleate), a reaction product of an oleic acid moiety and the prochloraz backbone, was identified for the first time. The quantification of prochloraz, icpame-oleate, imidazole, and 2,4,6-trichlorophenol demonstrated the dependency of the degradation process on temperature, heating duration, and type of oil. The obtained results in this study show the enormous impact of high temperature food processing on the fate of pesticides. The necessity to consider matrix related reactions in pesticide regulation is emphasized, and the suitability of the OECD 507 guideline is questioned. Concerning possible toxicological risks of novel degradation products, future studies will have to assess potential hazards or opportunities of food processing, ultimately yielding in safer food.

A combined FSTRA-shotgun proteomics approach to identify molecular changes in zebrafish upon chemical exposure.

The fish short-term reproduction assay (FSTRA) is a common in vivo screening assay for assessing endocrine effects of chemicals on reproduction in fish. However, the current reliance on measures such as egg number, plasma vitellogenin concentration and morphological changes to determine endocrine effects can lead to false labelling of chemicals with non-endocrine modes- of-action. Here, we integrated quantitative liver and gonad shotgun proteomics into the FSTRA in order to investigate the causal link between an endocrine mode-of-action and adverse effects assigned to the endocrine axis. Therefore, we analyzed the molecular effects of fadrozole-induced aromatase inhibition in zebrafish (Danio rerio). We observed a concentration-dependent decrease in fecundity, a reduction in plasma vitellogenin concentrations and a mild oocyte atresia with oocyte membrane folding in females. Consistent with these apical measures, proteomics revealed a significant dysregulation of proteins involved in steroid hormone secretion and estrogen stimulus in the female liver. In the ovary, the deregulation of estrogen synthesis and binding of sperm to zona pellucida were among the most significantly perturbed pathways. A significant deregulation of proteins targeting the transcriptional activity of estrogen receptor (esr1) was observed in male liver and testis. Our results support that organ- and sex-specific quantitative proteomics represent a promising tool for identifying early gene expression changes preceding chemical-induced adverse outcomes. These data can help to establish consistency in chemical classification and labelling.

Fate of a perfluoroalkyl acid mixture in an agricultural soil studied in lysimeters.

Perfluoroalkyl acids (PFAAs) are environmental contaminants of concern in both food and drinking water. PFAA fate in agricultural soil is an important determinant of PFAA contamination of groundwater and crops. The fate of C4-C14 perfluorinated carboxylic acids (PFCAs) and two perfluorinated sulfonic acids (PFSAs) in an agricultural soil was studied in a field lysimeter experiment. Soil was spiked with PFAAs at four different levels and crops were planted. PFAA concentrations in soil were measured at the beginning and end of the growing season. Lysimeter drainage water was collected and analysed. The concentrations of all PFAAs decreased in the surface soil during the growing season, with the decrease being negatively correlated with the number of fluorinated carbons in the PFAA molecule. PFAA transfer to the drainage water was also negatively correlated with the number of fluorinated carbons. For the C11-C14 PFCAs most of the decrease in soil concentration was attributed to the formation of non-extractable residues. For the remaining PFAAs leaching was the dominant removal process. Leaching was concentration dependent, with more rapid removal from the soils spiked with higher PFAA levels. Model simulations based on measured Kd values under-predicted removal by leaching. This was attributed to mixture effects that reduced PFAA sorption to soil.

First evidence of anticoagulant rodenticides in fish and suspended particulate matter: spatial and temporal distribution in German freshwater aquatic systems.

Anticoagulant rodenticides (ARs) have been used for decades for rodent control worldwide. Research on the exposure of the environment and accumulation of these active substances in biota has been focused on terrestrial food webs, but few data are available on the impact of ARs on aquatic systems and water organisms. To fill this gap, we analyzed liver samples of bream (Abramis brama) and co-located suspended particulate matter (SPM) from the German Environmental Specimen Bank (ESB). An appropriate method was developed for the determination of eight different ARs, including first- and second-generation ARs, in fish liver and SPM. Applying this method to bream liver samples from 17 and 18 sampling locations of the years 2011 and 2015, respectively, five ARs were found at levels above limits of quantifications (LOQs, 0.2 to 2 µg kg-1). For 2015, brodifacoum was detected in 88% of the samples with a maximum concentration of 12.5 µg kg-1. Moreover, difenacoum, bromadiolone, difethialone, and flocoumafen were detected in some samples above LOQ. In contrast, no first generation AR was detected in the ESB samples. In SPM, only bromadiolone could be detected in 56% of the samples at levels up to 9.24 µg kg-1. A temporal trend analysis of bream liver from two sampling locations over a period of up to 23 years revealed a significant trend for brodifacoum at one of the sampling locations.

Bioconcentration studies with the freshwater amphipod Hyalella azteca: are the results predictive of bioconcentration in fish?

Bioconcentration factors (BCF) for regulatory purposes are usually determined by fish flow-through tests according to technical guidance document OECD 305. Fish bioconcentration studies are time consuming, expensive, and use many laboratory animals. The aim of this study was to investigate whether the freshwater amphipod Hyalella azteca can be used as an alternative test organism for bioconcentration studies. Fourteen substances of different hydrophobicity (log Kow 2.4-7.6) were tested under flow-through conditions to determine steady state and kinetic bioconcentration factors (BCFss and BCFk). The results were compared with fish BCF estimates for the same substances described in the literature to show the relationship between both values. Bioconcentration studies with the freshwater amphipod H. azteca resulted in BCF estimates which show a strong correlation with fish BCF values (r2 = 0.69). Hyalella BCF values can be assessed in accordance with the regulatory B criterion (BCF > 2000, i.e., REACH) and thereby enable the prediction of B or non-B classification in the standard fish test. Therefore, H. azteca has a high potential to be used as alternative test organism to fish for bioconcentration studies.

Four Chemical Trends Will Shape the Next Decade's Directions in Perfluoroalkyl and Polyfluoroalkyl Substances Research.

Per- and polyfluoroalkyl substances (PFAS) represent a versatile group of ubiquitously occurring chemicals of increasing regulatory concern. The past years lead to an ever expanding portfolio of detected anthropogenic PFAS in numerous products encountered in daily life. Yet no clear picture of the full range of individual substance that comprise PFAS is available and this challenges analytical and engineering sciences. Authorities struggle to cope with uncertainties in managing risk of harm posed by PFAS. This is a result of an incomplete understanding of the range of compounds that they comprise in differing products. There are analytical uncertainties identifying PFAS and estimating the concentrations of the total PFAS load individual molecules remain unknown. There are four major trends from the chemical perspective that will shape PFAS research for the next decade. Mobility: A wide and dynamic distribution of short chain PFAS due to their high polarity, persistency and volatility.Substitution of regulated substances: The ban or restrictions of individual molecules will lead to a replacement with substitutes of similar concern.Increase in structural diversity of existing PFAS molecules: Introduction of e.g., hydrogens and chlorine atoms instead of fluorine, as well as branching and cross-linking lead to a high versatility of unknown target molecules.Unknown "Dark Matter": The amount, identity, formation pathways, and transformation dynamics of polymers and PFAS precursors are largely unknown. These directions require optimized analytical setups, especially multi-methods, and semi-specific tools to determine PFAS-sum parameters in any relevant matrix.

Hexabromocyclododecane diastereomers in fish and suspended particulate matter from selected European waters-trend monitoring and environmental quality standard compliance.

The brominated flame retardant hexabromocyclododecane (HBCD) was monitored in fish and sediment (from one lake) or suspended particulate matter (SPM; from five rivers) at European freshwater sites to study the effects of reduction measures implemented by HBCD producers and users in recent years. Bream (Abramis brama) were sampled annually between 2007 and 2013 in the rivers Götaälv/SE, Rhône/FR, Western Scheldt/NL, Mersey/UK, and Tees/UK and in Lake Belau/DE. Sediment/SPM was taken every second year between 2008 and 2014. HBCD was analyzed by LC/MS/MS allowing the determination of the alpha-, beta-, and gamma-diastereomers. For most sites, a decrease in ∑HBCD was observed in fish (e.g., in the Rhône and Western Scheldt by about 80 and 60%, respectively, with significantly decreasing trends, p < 0.01). In the Rhône, HBCD also decreased in SPM. At the sampling site in the Tees which was impacted by a former HBCD point source, fish HBCD levels decreased only after a major flood event in 2013. While fish data indicate a decline in environmental HBCD concentrations at most sites with diffuse emissions, SPM data were less conclusive. The European environmental quality standard for HBCD in fish of 167 µg kg-1 wet weight was met by all fish samples in 2013.

Detection of tetrabromobisphenol A and its mono- and dimethyl derivatives in fish, sediment and suspended particulate matter from European freshwaters and estuaries.

An analytical method was developed for the determination of tetrabromobisphenol A (TBBPA), 3,3',5,5'-tetrabromobisphenol-A-monomethyl ether (MM-TBBPA) and 3,3',5,5'-tetrabromobisphenol-A-dimethyl ether (DM-TBBPA), and its valid application on fish muscle matrix (bream and sole), suspended particulate matter (SPM) and surface sediment layer samples, using only 0.5 g sample material, is demonstrated. Here, for the first time, DM-TBBPA could be determined by an LC-MS/MS-based method applying atmospheric pressure photoionization (APPI), using the same sample extracts for all three analytes. Samplings covered freshwater fish (bream; annually, period 2007-2013) and SPM or sediment (every second year in the period 2008-2014) at selected European sites (rivers: Tees/UK, Mersey/UK, Western Scheldt/NL, Götaälv/SE, Rhône/FR; Lake Belau/DE). TBBPA could be quantified in 13 of 36 bream samples (range about 0.5-1.2 µg kg-1 ww) and 7 of 7 sole muscle samples (range about 0.5-0.7 µg kg-1 ww). Further, it could be quantified in 11 of the 14 SPM samples (range about 0.5-9.4 µg kg-1 dw) and in both of the surface sediment layer samples (2.3-2.6 µg kg-1 dw). MM-TBBPA could be quantified in 12 of 36 bream and 4 of 7 sole muscle samples (range about 0.8-1.8 µg kg-1 ww). Further, it could be quantified in 10 of the 14 river SPM samples (range about 2.3-4.5 µg kg-1 dw) and in both lake surface sediment layer samples (5.2-5.5 µg kg-1 dw). DM-TBBPA was rarely detectable and could not be quantified above the limit of quantification in any sample.

OR2M3: A Highly Specific and Narrowly Tuned Human Odorant Receptor for the Sensitive Detection of Onion Key Food Odorant 3-Mercapto-2-methylpentan-1-ol.

The detection of key food odorants appears to be an important capability of odorant receptors. Here, thiols occupy an outstanding position among the 230 known key food odorants because of their very low odor thresholds. Members of the homologous series of 3-mercapto-2-methylalkan-1-ols have been described as onion key food odorants or food constituents and are detected at logarithmically different thresholds. 3-Mercapto-2-methylpentan-1-ol being the only key food odorant within this series also has the lowest odor threshold. Most odorants typically activate combinations of odorant receptors, which may be narrowly or broadly tuned. Consequently, a specific receptor activation pattern will define an odor quality. In contrast, here we show that just 1 of the 391 human odorant receptors, OR2M3, responded exclusively to 3-mercapto-2-methylpentan-1-ol of the 190 key food odorants tested, with a half maximal effective concentration at submicromolar concentration. Moreover, neither the Denisovan OR2M3 nor the closest OR2M3 homologs from five species did respond to this compound. This outstanding specificity of extremely narrowly tuned human OR2M3 can explain both odor qualities and odor threshold trend within a homologous series of 3-mercapto-2-methylalkan-1-ols and suggests a modern human-specific, food-related function of OR2M3 in detecting a single onion key food odorant.

Critical micelle concentration values for different surfactants measured with solid-phase microextraction fibers.

The amphiphilic nature of surfactants drives the formation of micelles at the critical micelle concentration (CMC). Solid-phase microextraction (SPME) fibers were used in the present study to measure CMC values of 12 nonionic, anionic, cationic, and zwitterionic surfactants. The SPME-derived CMC values were compared to values determined using a traditional surface tension method. At the CMC of a surfactant, a break in the relationship between the concentration in SPME fibers and the concentration in water is observed. The CMC values determined with SPME fibers deviated by less than a factor of 3 from values determined with a surface tension method for 7 out of 12 compounds. In addition, the fiber-water sorption isotherms gave information about the sorption mechanism to polyacrylate-coated SPME fibers. A limitation of the SPME method is that CMCs for very hydrophobic cationic surfactants cannot be determined when the cation exchange capacity of the SPME fibers is lower than the CMC value. The advantage of the SPME method over other methods is that CMC values of individual compounds in a mixture can be determined with this method. However, CMC values may be affected by the presence of compounds with other chain lengths in the mixture because of possible mixed micelle formation. Environ Toxicol Chem 2016;35:2173-2181. © 2016 SETAC.

Perfluoroalkyl and polyfluoroalkyl substances in consumer products.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in a wide range of products of all day life. Due to their toxicological potential, an emerging focus is directed towards their exposure to humans. This study investigated the PFAS load of consumer products in a broad perspective. Perfluoroalkyl sulfonic acids (C4, C6-C8, C10-PFSA), carboxylic acids (C4-C14-PFCA) and fluorotelomer alcohols (4:2, 6:2; 8:2 and 10:2 FTOH) were analysed in 115 random samples of consumer products including textiles (outdoor materials), carpets, cleaning and impregnating agents, leather samples, baking and sandwich papers, paper baking forms and ski waxes. PFCA and PFSA were analysed by HPLC-MS/MS, whereas FTOH were detected by GC/CI-MS. Consumer products such as cleaning agents or some baking and sandwich papers show low or negligible PFSA and PFCA contents. On the other hand, high PFAS levels were identified in ski waxes (up to about 2000 µg/kg PFOA), leather samples (up to about 200 µg/kg PFBA and 120 µg/kg PFBS), outdoor textiles (up to 19 µg/m(2) PFOA) and some other baking papers (up to 15 µg/m(2) PFOA). Moreover, some test samples like carpet and leather samples and outdoor materials exceeded the EU regulatory threshold value for PFOS (1 µg/m(2)). A diverse mixture of PFASs can be found in consumer products for all fields of daily use in varying concentrations. This study proves the importance of screening and monitoring of consumer products for PFAS loads and the necessity for an action to regulate the use of PFASs, especially PFOA, in consumer products.

Nature's chemical signatures in human olfaction: a foodborne perspective for future biotechnology.

The biocatalytic production of flavor naturals that determine chemosensory percepts of foods and beverages is an ever challenging target for academic and industrial research. Advances in chemical trace analysis and post-genomic progress at the chemistry-biology interface revealed odor qualities of nature's chemosensory entities to be defined by odorant-induced olfactory receptor activity patterns. Beyond traditional views, this review and meta-analysis now shows characteristic ratios of only about 3 to 40 genuine key odorants for each food, from a group of about 230 out of circa 10 000 food volatiles. This suggests the foodborn stimulus space has co-evolved with, and roughly match our circa 400 olfactory receptors as best natural agonists. This perspective gives insight into nature's chemical signatures of smell, provides the chemical odor codes of more than 220 food samples, and beyond addresses industrial implications for producing recombinants that fully reconstruct the natural odor signatures for use in flavors and fragrances, fully immersive interactive virtual environments, or humanoid bioelectronic noses.

A hit map-based statistical method to predict best ligands for orphan olfactory receptors: natural key odorants versus "lock picks".

Smell is a multidimensional chemical sense. It creates a perception of our odorous environment by integrating the information of a plethora of volatile chemicals with other sensory inputs, emotions and memories. We are almost always exposed to odorant mixtures, not just single chemicals. Olfactory processing of complex odorant mixtures, such as coffee or wine, first is decoded at the site of perception by the hundreds of different olfactory receptor types, each residing in the cilia of their olfactory sensory neurons in the nose. Often, only a few odorants from many are essential to determine complex olfactory perception. But merely using the chemical structure of odorants is insufficient to identify and predict characteristic odor qualities and low odor thresholds. An understanding of odorant coding critically depends on knowledge about the interaction of key odorants of biologically relevant odor bouquets with their best cognate receptors. Here, we describe a hit map-based method of correlating the information content of all bioassay-tested odorants with their cognate odorant-receptor frequency in four phylogenetic subsets of human olfactory/chemosensory receptors.