Priority Hazardous Substances Research Articles

Sustainable approach for recycling seafood wastes for the removal of priority hazardous substances (Hg and Cd) from water

Mercury and cadmium are considered by the water framework directive priority hazardous substances. In this work, the capacity of crab carapace and clam shell wastes to remove mercury and cadmium from water was evaluated under batch conditions, for realistic contamination scenarios in monometallic and binary solutions. The results evidenced that in monometallic solutions and under studied operational conditions, both biosorbents can achieve Hg2+ removal efficiencies higher than 80% and the kinetic process is well described by two of the most widely used equations, the pseudo-second order and the Elovich model. In terms of biosorption equilibrium, crab carapace and clam shell wastes displayed very distinct behaviours. While clam shells achieve the complete monolayer coverage and the isotherm is well described by the Langmuir model, crab carapace powder display a more unusual behaviour, that is well described by the BET isotherm, and is characterized by an almost convex shape to the concentration axis, with an infinite slope for an Hg2+ concentration in solution around 25μg/L. In binary solutions, both wastes are able to uptake simultaneously Hg2+ and Cd2+, however the uptake of Hg2+ was inhibited in some extent, attributed to the high kinetic and equilibrium selectivities of the bio-wastes for cadmium.

Trace Amount of SnO2-Decorated ZnSn(OH)6 as Highly Efficient Photocatalyst for Decomposition of Gaseous Benzene: Synthesis, Photocatalytic Activity, and the Unrevealed Synergistic Effect between ZnSn(OH)6 and SnO2

It is still a challenge to develop a high-performance photocatalyst for the abatement of aromatic compounds like benzene (C6H6), which has been regarded as a priority hazardous volatile organic compound substance in the indoor atmosphere. Zinc hydroxystannate (ZnSn(OH)6, ZHS) is a promising material for this application. However, the key structural features that are responsible for the high activity are still ambiguous. To address this issue, a series of ZHS with different surface properties were hydrothermally synthesized by varying the treatment temperature and the solution pH. Although ZHS can be readily synthesized under a mild reaction condition (temp 90–120 °C, pH 4–10), most of the samples were contaminated by a trace amount of low-crystallized SnO2. Pristine ZHS can only be produced in a strong alkaline solution (pH 13). The sample prepared at 120 °C in a pH 10 solution shows the highest activity for the degradation of gaseous C6H6 and an efficiency almost 6 times higher than P25 (TiO2). More impo...

Imposex in Nassarius nitidus (Jeffreys, 1867) as a possible investigative tool to monitor butyltin contamination according to the Water Framework Directive: A case study in the Venice Lagoon (Italy)

Butyltin (TBT, DBT, and MBT) effects on molluscs, especially endocrine disruption in bivalves and gastropods, have been widely investigated. Imposex, the superimposition of male characters onto female gonochoristic Caenogastropods, is the most studied biological effect of TBT. TBT compounds are among the priority hazardous substances within Directives 2000/60/EC (WFD) and 2008/105/EC. The Environmental Quality Standards (EQSs) set by the WFD for TBT are quite difficult to quantify by means of chemical analysis, without the use of expensive and high performance methods. Assuming that EQSs set for TBT were derived from evidence of imposex development at very low concentrations, this specific biomarker could be used as an indirect measure of assessing levels of bioavailable BTs. Therefore, this study aims to validate the use of imposex development as an investigative tool to monitor the bioavailable fraction of BTs within the WFD, by comparing imposex levels and BT concentrations in Nassarius nitidus from the Venice Lagoon.BT concentrations and imposex levels in N. nitidus, collected in 2013, had decreased when compared to previous studies in the same area. Both VDSI and RPLI correlated positively with BT body burden in females, confirming that imposex is a valid tool to monitor bioavailable BTs. However, TBT is still a matter of concern in the Venice Lagoon, as TBT concentrations were still higher than its degradation products suggesting recent fresh TBT inputs in the studied area. To propose imposex levels as an indicator of the impact of BTs within the WFD, classification class boundaries and Ecological Quality Ratios were introduced.As a preliminary attempt, imposex levels were also compared to the OSPAR Commission EcoQOs which linked imposex levels in Nassarius reticulatus with TBT concentrations in water. Based on this comparison the degree of imposex development in the Venice Lagoon suggested that TBT concentrations in water should be over the EQS-AA concentration and, at one site, also over the EQS-MAC.From all the results obtained in this work, it appears that imposex evaluation in N. reticulatus could give information about the ecological status regarding BT compounds under the WFD and also be used to monitor their effects and support chemical analyses until more sensitive methods become available.

A simple, low cost GC/MS method for the sub-nanogram per litre measurement of organotins in coastal water

Tributyltin (TBT) is a legacy pollutant in the aquatic environment, predominantly from its use in anti-foulant paints and is listed as a priority hazardous substance in the European Union’s Water Framework Directive (WFD). Measuring low concentrations of TBT and other organotins (e.g. monobutyltin (MBT), dibutyltin (DBT), diphenyltin (DPhT) and triphenyltin (TPhT)) at sub ng/L concentrations in coastal waters using standard laboratory instrumentation is very challenging. Conventional, low injection volume gas chromatography/mass spectrometry (GC/MS) combined with liquid-liquid extraction typically achieves limits of detection for TBT ∼10ngL−1. We describe a simple, programmed temperature vaporisation-large injection volume (50μL), GC/MS selected ion monitoring method for measuring DBT, TBT, DPhT and TPhT in coastal waters at lower concentrations. Quantification of MBT was not possible using these injection volumes but was achieved using a 10μL injection volume together with a reduced injection speed.This new approach offers:•When using a 50μL injection, limits of detection=0.70ngL−1 and limits of quantification=2.1ngL−1 for TBT were achieved in derivatised standards.•Recoveries of TBT and TPhT from coastal water >97%.•Time consuming, off-line sample pre-concentration methods are unnecessary.

Rapid analysis of diclofenac in freshwater and wastewater by a monoclonal antibody-based highly sensitive ELISA

The non-steroidal anti-inflammatory drug (NSAID) diclofenac (DCF) is found worldwide in the aqueous environment. Therefore, it has raised increased public concern on potential long-term impact on human health and wildlife. The importance of DCF has been emphasized by the European Union recently by including this pharmaceutical in the first watch list of priority hazardous substances in order to gather Union-wide monitoring data. Rapid and cheap methods of analysis are therefore required for fresh and wastewater monitoring with high sample load. Here, for the first time, well-characterized monoclonal antibodies (mAbs) against DCF were generated and a highly sensitive ELISA developed. The best antibody (mAb 12G5) is highly affine (KD = 1.5 × 10(-10) M), stable to potential matrix interferences such as pH value (pH range 5.2-9.2), calcium ion concentration (up to 75mg/L), and humic acid content (up to 20mg/L). The limit of detection (LOD, S/N = 3) and IC50 of the ELISA calibration curve were 7.8 and 44ng/L, respectively. The working range was defined between 11 and 180ng/L. On average, about 10% cross-reactivity (CR) was found for DCF metabolites 5-OH-DCF, 4'-OH-DCF, and DCF-acyl glucuronide, but other structurally related NSAIDs showed binding <1% compared to the parent compound. While DCF concentrations at the low ppt range were measured in river and lake water, higher values of 2.9 and 2.1μg/L were found in wastewater influents and effluents, respectively. These results could be confirmed by solid phase extraction combined with LC-MS.

A statistical evaluation of the safety factor and species sensitivity distribution approaches to deriving environmental quality guidelines.

The species sensitivity distribution (SSD) distribution approach to estimating water quality guidelines (WQGs) is the preferred method in all jurisdictions reviewed (Australia, Canada, New Zealand, Organisation for Economic Co-operation and Development [OECD] members, South Africa, United States) and is one of the recommended methods for European Commission members for 33 priority and priority hazardous substances. In the event that jurisdiction-specific criteria for data quality, quantity, and taxonomic representation are not met, all of these jurisdictions endorse the use of additional safety factors (SFs) applied to either the SSD-based WQG or, the lowest suitable toxicity test endpoint. In Canada, the British Columbia Ministry of Environment endorses this latter approach as the preferred approach in the belief that so-derived WQGs are more protective than SSD-based WQGs. The level of protection afforded by the latter SF approach was evaluated by statistically sampling minima from random samples of the following distributions: normal, Gumbel, logistic, and Weibull, using a range of coefficients of variation (cVs) and applying the SFs of 2 or 10 used in British Columbia. The simulations indicate that the potentially affected fraction of species (PAF) can be as high as 20%, or, approach 0%. The PAF varies with sample size and CV. Because CVs can vary systematically with mode of toxic action, the PAF using SF-based WQGs can also vary systematically with analyte class. The varying levels of protection afforded by SF-based WQGs are generally inconsistent with the common water quality management goal that allows for a small degree of change under long-term exposure. The findings suggest that further efforts be made to develop high-quality WQGs that support informed decision making and are consistent with the environmental management goal instead of using SFs in the hope of achieving an acceptable but unknown, degree of environmental protection.

Parameters optimization using experimental design for headspace solid phase micro-extraction analysis of short-chain chlorinated paraffins in waters under the European water framework directive

The water framework directives (WFD 2000/60/EC and 2013/39/EU) force European countries to monitor the quality of their aquatic environment. Among the priority hazardous substances targeted by the WFD, short chain chlorinated paraffins C10–C13 (SCCPs), still represent an analytical challenge, because few laboratories are nowadays able to analyze them. Moreover, an annual average quality standards as low as 0.4μgL−1 was set for SCCPs in surface water. Therefore, to test for compliance, the implementation of sensitive and reliable analysis method of SCCPs in water are required. The aim of this work was to address this issue by evaluating automated solid phase micro-extraction (SPME) combined on line with gas chromatography-electron capture negative ionization mass spectrometry (GC/ECNI–MS).Fiber polymer, extraction mode, ionic strength, extraction temperature and time were the most significant thermodynamic and kinetic parameters studied. To determine the suitable factors working ranges, the study of the extraction conditions was first carried out by using a classical one factor-at-a-time approach. Then a mixed level factorial 3×23 design was performed, in order to give rise to the most influent parameters and to estimate potential interactions effects between them. The most influent factors, i.e. extraction temperature and duration, were optimized by using a second experimental design, in order to maximize the chromatographic response.At the close of the study, a method involving headspace SPME (HS-SPME) coupled to GC/ECNI-MS is proposed. The optimum extraction conditions were sample temperature 90°C, extraction time 80min, with the PDMS 100μm fiber and desorption at 250°C during 2min. Linear response from 0.2ngmL−1 to 10ngmL−1 with r2=0.99 and limits of detection and quantification, respectively of 4pgmL−1 and 120pgmL−1 in MilliQ water, were achieved. The method proved to be applicable in different types of waters and show key advantages, such as simplicity, automation and sensitivity, required for the monitoring programs linked to the WFD.

Tributyltin pollution biomonitoring under the Water Framework Directive: Proposal of a multi-species tool to assess the ecological quality status of EU water bodies

The Water Framework Directive (WFD) is a key legislative action developed by the European Union in order to protect aquatic ecosystems. One of the concerning pollutants, listed in this directive as a priority hazardous substance, is tributyltin (TBT), a biocide largely used in antifouling paints and identified as a causative agent of imposex/intersex in gastropods. In order to integrate TBT pollution monitoring within this legislative framework, a practical exercise is here proposed to assess the evolution of surface water ecological status in Ria de Aveiro (NW Portugal). Three bioindicators – the caenogastropods Nucella lapillus, Nassarius reticulatus and Littorina littorea – were used under the general WFD benthic invertebrate quality element, and the vas deferens sequence index (VDSI) and the intersex index (ISI) were selected as biomarkers for the purpose of assessing the condition of this quality element regarding the impact of TBT pollution. Levels of VDSI in N. lapillus and N. reticulatus, and ISI in L. littorea, were surveyed in 2013 and compared with previous data available for the same species and study area in 1998 and 2005, providing a time lapse for a period of 15 years. VDSI and ISI values were converted into Ecological Quality Ratios (EQR) and EQR boundaries were set for each species in order to define the five ecological status classes (High, Good, Moderate, Poor and Bad). We propose N. lapillus as key bioindicator, however the combined use of further species is very useful to cover a wider study area. Based on the proposed method, it is concluded that the ecological status of the surface waters surveyed in Ria de Aveiro, concerning the impact of TBT pollution on the above benthic invertebrate taxa, improved considerably since 1998 and achieved a Good Ecological Status in 2013, thus meeting the WFD environmental objectives for this priority hazardous substance even before 2015.

Effectiveness of measures adopted for the reduction of nonylphenol emission in European river basins: a case study of the River Lambro, Northern Italy

According to the Water Framework Directive 2000/60/EC, nonylphenol (NP) has been included in the list of priority hazardous substances and subject to cessation or phasing out of discharges, emissions and losses within an appropriate timetable not exceeding 20 years. The present work analyzed monitoring data on NP and its precursors (mono- and di-ethoxylates, nonylphenol-mono-ethoxylate and nonylphenol-di-ethoxylate) collected in a highly impacted river basin in Northern Italy in order to assess the effectiveness of the adopted measures for NP reduction, during two monitoring campaigns in 2003/04 and 2009/10, respectively, before and after the entry into operation of three new wastewater treatment plants (WWTPs) in Milan. The River Lambro is the main source of pollutants also for the River Po and the Adriatic Sea. Data collected in the present work showed that in the last 7 years the reduction of the different analytes was from 70% to 90%. Most of the reduction can be attributed to the substitution of nonylphenolethoxylates in industrial uses as demonstrated by a survey in the textile industrial district. The entry into operation of the new municipal WWTPs in Milan contributes about 10% of the reduction of the total NP load discharged by the River Lambro.

Ecological modelling and toxicity data coupled to assess population recovery of marine amphipod Gammarus locusta: Application to disturbance by chronic exposure to aniline

A population agent-based model of marine amphipod Gammarus locusta was designed and implemented as a basis for ecological risk assessment of chemical pollutants impairing life-history traits at the individual level. We further used the model to assess the toxic effects of aniline (a priority hazardous and noxious substance, HNS) on amphipod populations using empirically-built dose-response functions derived from a chronic bioassay that we previously performed with this species. We observed a significant toxicant-induced mortality and adverse effects in reproductive performance (reduction of newborn production) in G. locusta at the individual level. Coupling the population model with the toxicological data from the chronic bioassay allowed the projection of the ecological costs associated with exposure to aniline that might occur in wild populations. Model simulations with different scenarios indicated that even low level prolonged exposure to the HNS aniline can have significant long-term impacts on G. locusta population abundance, until the impacted population returns to undisturbed levels. This approach may be a useful complement in ecotoxicological studies of chemical pollution to transfer individual-collected data to ecological-relevant levels.

DISCHARGE WATERS: DETERMINATION OF POLYCYCLIC AROMATIC HYDROCARBON (PAH) LEVELS BY A GC-MS/MS METHOD

The aim of this work was to determine polycyclic aromatic hydrocarbon (PAH) levels in discharge waters from municipal and industrial treatment plants. For this purpose a simple and sensitive method for the analysis of 16 PAHs at ultra-trace levels in water has been developed and validated using liquid-liquid extraction (LLE) and gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The total PAH content was in the range 100-800 ng L-1 for samples from surface treatment (ST) industries against 700-2000 ng L-1 for samples from municipal plants. Among PAHs, maximal values of 850 ng L-1 and 340 ng L-1 were obtained for phenanthrene in municipal and industrial discharge waters, respectively. Furthermore, the environmental quality standard of the Water Framework Directive expressed as maximal allowable concentrations in municipal treated waters was only overshot for benzo[g, h, i]perylene, a priority substance, and for fluoranthene, classified as a priority hazardous substance.

N-acetyl-β-d-glucosaminidase activity in feral Carcinus maenas exposed to cadmium

Cadmium is a priority hazardous substance, persistent in the aquatic environment, with the capacity to interfere with crustacean moulting. Moulting is a vital process dictating crustacean growth, reproduction and metamorphosis. However, for many organisms, moult disruption is difficult to evaluate in the short term, what limits its inclusion in monitoring programmes. N-acetyl-β-d-glucosaminidase (NAGase) is an enzyme acting in the final steps of the endocrine-regulated moulting cascade, allowing for the cast off of the old exoskeleton, with potential interest as a biomarker of moult disruption. This study investigated responses to waterborne cadmium of NAGase activity of Carcinus maenas originating from estuaries with different histories of anthropogenic contamination: a low impacted and a moderately polluted one. Crabs from both sites were individually exposed for seven days to cadmium concentrations ranging from 1.3 to 2000μg/L. At the end of the assays, NAGase activity was assessed in the epidermis and digestive gland. Detoxification, antioxidant, energy production, and oxidative stress biomarkers implicated in cadmium metabolism and tolerance were also assessed to better understand differential NAGase responses: activity of glutathione S-transferases (GST), glutathione peroxidase (GPx) glutathione reductase (GR), levels of total glutathiones (TG), lipid peroxidation (LPO), lactate dehydrogenase (LDH), and NADP+-dependent isocitrate dehydrogenase (IDH). Animals from the moderately polluted estuary had lower NAGase activity both in the epidermis and digestive gland than in the low impacted site. NAGase activity in the epidermis and digestive gland of C. maenas from both estuaries was sensitive to cadmium exposure suggesting its usefulness for inclusion in monitoring programmes. However, in the digestive gland NAGase inhibition was found in crabs from the less impacted site but not in those from the moderately contaminated one. Altered glutathione levels were observed in cadmium-treated crabs from the contaminated site possibly conferring enhanced tolerance to these animals through its chelator action. Investigation of enhanced tolerance should thus be accounted for in monitoring programmes employing NAGase as biomarker to avoid data misinterpretation.

Mercury leaching from hazardous industrial wastes stabilized by sulfur polymer encapsulation

European Directive 2013/39/EU records mercury as a priority hazardous substance. Regulation n° 2008/1102/EC banned the exportation of mercury and required the safe storage of any remaining mercury compounds. The present work describes the encapsulation of three wastes containing combinations of HgS, HgSe, HgCl2, HgO2, Hg3Se2Cl2, HgO and Hg0, according to patent of Spanish National Research Council WO2011/029970A2. The materials obtained were subjected to leaching tests according to standards UNE-EN-12457 and CEN/TS 14405:2004. The results are compared with the criteria established in the Council Decision 2003/33/EC for the acceptance of waste at landfills. The Hg concentrations of all leachates were <0.01mgHg/kg for a liquid/solid ratio of 10l/kg. All three encapsulated materials therefore meet the requirements for storage in inert waste landfills.

Isomer-specific biodegradation of nonylphenol in an activated sludge bioreactor and structure–biodegradability relationship

Nonylphenol (NP), one of the priority hazardous substances, is in fact a mixture of numerous isomers. It is inconclusive whether or not biodegradation during wastewater treatment process is isomer-specific, leading to the environmental release of NP in different isomer profiles. In this study, we evaluated the isomer selectivity of 19 NP isomers in a laboratory-scale continuous flow conventional activated sludge bioreactor under various operational conditions. The removal efficiency of NP isomers ranged from 90 to 99%, depending on the operational conditions and isomer structures. Isomer selective biodegradation resulted in the increase of composition of recalcitrant isomers, such as, NP193a/b, NP110a and NP194 in the effluent. Moreover, biodegradability was related to the bulkiness of α-substituents and followed α-dimethyl > α-ethyl-α-methyl > α-methyl-α-n-propyl > α-iso-propyl-α-methyl. Steric effect index, a quantitative descriptor of steric hindrance, was linearly correlated with residues of NP isomers in the effluent (R2 = 0.76). Decrease of temperature to 10 °C decreased the overall biodegradability and also enhanced the relative enrichment of recalcitrant isomers. These findings suggest that isomer compositions of NP entering the environment may be different from those in technical mixtures and that isomeric selectivity should be taken into account to better understand the occurrence, fate, and ecological risks of NP.

Ranking COMMPS Chemical Substances by an Improved POT/RLE Approach

The combined monitoring-based and modeling-based priority setting (COMMPS) provides a procedure for the identification of priority hazardous substances outlined in the Working Document (ENV/191000/01 of January 16, 2001). This procedure is based on scoring a set of criteria which individually make substances more or less hazardous. The way scores are weighted and combined has been established by a panel of experts. Different authors outlined how such a procedure might be affected by subjectiveness of judgment, and alternative solutions based on partial order theory (POT) and random linear extensions (RLE) have been suggested. This method consists of generating a set of RLE and of averaging the rank given to each substance, so that a total order could be determined. Any POT/RLE approach must face the issue of covering as much as possible the space of linear extensions that, in the case of the 85 substances considered by COMMPS, becomes extremely large, and an exhaustive generation of linear extension is not feasible. Therefore, having a faster algorithm would help to consider a larger number of linear extensions in a given time frame. In this paper, we discuss this problem, and we outline a possible solution.

Competitive Removal of Cd2+ and Hg2+ Ions from Water Using Titanosilicate ETS-4: Kinetic Behaviour and Selectivity

Mercury and cadmium are priority hazardous substances. Some titanosilicates have been tested for the removal of Cd2+ and Hg2+ from single solutions by ion exchange. In this work, the competition between both contaminants for the exchanger binding sites of titanosilicate Engelhard titanosilicate material number 4 (ETS-4) was studied by performing batch experiments with aqueous solutions containing the two counter ions. The results evidenced the large capacity of ETS-4 and shown that the cadmium(II) diffusivity through the sorbent is higher than that of mercury(II). Furthermore, the ETS-4 exhibited higher kinetic and equilibrium selectivities for Cd2+, which attained values in the ranges 8.9–12.5 and 7.9–12.8, respectively. With respect to modelling, the pseudo-second-order equation described successfully the competitive removal of Cd2+ and Hg2+.

Removal of selected pesticides by adsorption

Abstract The paper is focused on the removal of selected priority hazardous substances. Five chlorinated pesticides, i.e. hexachlorobenzene (HCHB), hexachlorobutadiene (HCHBD), lindane (LIN), pentachlorobenzene (PCHB) and heptachlor (HCH) were selected as model pollutants. Higher volatility is characteristic for these substances. Adsorption of these pollutants on granular activated carbon (GAC), zeolite (Zeo) and activated sludge (AS) was investigated. The effect of contact time on the removal efficiency of studied substances was investigated. From results of the work it follows that the highest removal efficiency of studied substances was achieved by the adsorption on activated sludge. This was followed by adsorption efficiency on zeolite. The lowest removal efficiency was measured for adsorption on granular activated carbon.

Determination of priority pollutants in aqueous samples by dispersive liquid–liquid microextraction

A dispersive liquid–liquid microextraction (DLLME) method followed by high-performance liquid chromatography–triple quadrupole mass spectrometry has been developed for the simultaneous determination of linear alkylbenzene sulfonates (LAS C10, C11, C12, and C13), nonylphenol (NP), nonylphenol mono- and diethoxylates (NP1EO and NP2EO), and di-(2-ethylhexyl)phthalate (DEHP). The applicability of the method has been tested by the determination of the above mentioned organic pollutants in tap water and wastewater. Several parameters affecting DLLME, such as, the type and volume of the extraction and disperser solvents, sample pH, ionic strength and number of extractions, have been evaluated. Methanol (1.5mL) was selected among the six disperser solvent tested. Dichlorobenzene (50μL) was selected among the four extraction solvent tested. Enrichment factor achieved was 80. Linear ranges in samples were 0.01–3.42μg L−1 for LAS C10–13 and NP2EO, 0.09–5.17μgL−1 for NP1EO, 0.17–9.19μgL−1 for NP and 0.40–17.9μgL−1 for DEHP. Coefficients of correlation were higher than 0.997. Limits of quantitation in tap water and wastewater were in the ranges 0.009–0.019μgL−1 for LAS, 0.009–0.091μgL−1 for NP, NP1EO and NP2EO and 0.201–0.224μgL−1 for DEHP. Extraction recoveries were in the range from 57 to 80%, except for LAS C10 (30–36%). The method was successfully applied to the determination of these pollutants in tap water and effluent wastewater from Seville (South of Spain). The DLLME method developed is fast, easy to perform, requires low solvent volumes and allows the determination of the priority hazardous substances NP and DEHP (Directive 2008/105/EC).

Contemporary Fraction of bis(2-ethylhexyl) Phthalate in Stilton Cheese by Accelerator Mass Spectrometry

Measurements of the radiocarbon abundance in 5 samples of bis(2-ethylhexyl) phthalate (DEHP) isolated from Stilton cheese were made by accelerator mass spectrometry (AMS) to determine the fraction of carbon originating from contemporary biogenic sources. DEHP is classified as a “priority hazardous substance” by the European Union, a probable human carcinogen by the United States Environmental Protection Agency, and is suspected to be a human endocrine disrupter. Measurement of its 14C abundance in a specific food indicates whether its presence is due to contamination from industrially synthesized DEHP or a naturally inherent component. A method was developed to determine the contemporary carbon fraction of DEHP in a fatty food matrix at concentrations of ≈0.14 mg/kg. Five 90-µg quantities of DEHP were extracted from 12 kg of Stilton cheese and isolated by silica gel, size exclusion, and high-performance liquid chromatography (HPLC). Masses of samples were determined by gas chromatography mass spectrometry (GC-MS) analyses prior to combustion and manometry afterwards. The purity of DEHP carbon mass in each isolate was determined by multivariate deconvolution of GCMS fragmentation spectra obtained from measurements of standards and isolates, and ranged from 88.0 ± 1.8% to 92.3 ± 1.1% ( n = 5, 1 σ ). Concurrently processed isolation method blanks contained from 0.15 ± 0.04 to 1.52 ± 0.06 µg ( n = 3, 1 σ ) DEHP per sample and significant quantities of pre- and post-chromatographic extraneous carbon contamination. The mean 14C-corrected contemporary carbon fraction of DEHP in the isolates was 0.235 ± 0.073 (1 σ ; and ± 0.091 at the 95% confidence level), revealing that the majority of DEHP in Stilton cheese results from anthropogenic sources, but with a significant naturally occurring component. DOI: 10.2458/azu_js_rc.55.16298

Contemporary Fraction of bis(2–ethylhexyl) Phthalate in Stilton Cheese by Accelerator Mass Spectrometry

Measurements of the radiocarbon abundance in 5 samples of bis(2–ethylhexyl) phthalate (DEHP) isolated from Stilton cheese were made by accelerator mass spectrometry (AMS) to determine the fraction of carbon originating from contemporary biogenic sources. DEHP is classified as a “priority hazardous substance” by the European Union, a probable human carcinogen by the United States Environmental Protection Agency, and is suspected to be a human endocrine disrupter. Measurement of its 14C abundance in a specific food indicates whether its presence is due to contamination from industrially synthesized DEHP or a naturally inherent component. A method was developed to determine the contemporary carbon fraction of DEHP in a fatty food matrix at concentrations of 0.14 mg/kg. Five 90–μg quantities of DEHP were extracted from 12 kg of Stilton cheese and isolated by silica gel, size exclusion, and high-performance liquid chromatography (HPLC). Masses of samples were determined by gas chromatography mass spectrometry (GC-MS) analyses prior to combustion and manometry afterwards. The purity of DEHP carbon mass in each isolate was determined by multivariate deconvolution of GCMS fragmentation spectra obtained from measurements of standards and isolates, and ranged from 88.0 ± 1.8% to 92.3 ± 1.1% (n = 5, 1σ). Concurrently processed isolation method blanks contained from 0.15 ± 0.04 to 1.52 ± 0.06 μg (n = 3, 1σ) DEHP per sample and significant quantities of pre- and post-chromatographic extraneous carbon contamination. The mean 14C-corrected contemporary carbon fraction of DEHP in the isolates was 0.235 ± 0.073 (1σ; and ± 0.091 at the 95% confidence level), revealing that the majority of DEHP in Stilton cheese results from anthropogenic sources, but with a significant naturally occurring component.