Persistent organic pollutants (POPs) are typically monitored via targeted mass spectrometry, which potentially identifies only a fraction of the contaminants actually present in environmental ...samples. With new anthropogenic compounds continuously introduced to the environment, novel and proactive approaches that provide a comprehensive alternative to targeted methods are needed in order to more completely characterize the diversity of known and unknown compounds likely to cause adverse effects. Nontargeted mass spectrometry attempts to extensively screen for compounds, providing a feasible approach for identifying contaminants that warrant future monitoring. We employed a nontargeted analytical method using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS) to characterize halogenated organic compounds (HOCs) in California Black skimmer (Rynchops niger) eggs. Our study identified 111 HOCs; 84 of these compounds were regularly detected via targeted approaches, while 27 were classified as typically unmonitored or unknown. Typically unmonitored compounds of note in bird eggs included tris(4-chlorophenyl)methane (TCPM), tris(4-chlorophenyl)methanol (TCPMOH), triclosan, permethrin, heptachloro-1'-methyl-1,2'-bipyrrole (MBP), as well as four halogenated unknown compounds that could not be identified through database searching or the literature. The presence of these compounds in Black skimmer eggs suggests they are persistent, bioaccumulative, potentially biomagnifying, and maternally transferring. Our results highlight the utility and importance of employing nontargeted analytical tools to assess true contaminant burdens in organisms, as well as to demonstrate the value in using environmental sentinels to proactively identify novel contaminants.
Photolytic degradation of decabromodiphenyl ether (BDE 209) has been observed in several matrices such as solvent/water mixtures, sediments, and soil; however, no studies have investigated the ...degradation potential of BDE 209 in house dust. In the present study, both a natural and a BDE 209–spiked dust material were exposed to sunlight for 200 cumulative h. Degradation of BDE 209 was observed in both matrices but was 35% greater in the spiked dust relative to the natural dust material. The pseudo‐first‐order degradation rates were 2.3 × 10−3 and 1.7 × 10−3 per hour for the spiked and natural dust, respectively. During the 200‐h exposure, as much as 38% of the original BDE 209 mass was degraded in the spiked dust, 25% of which could not be accounted for and was lost to unknown pathways and/or products. The remaining 13% was accounted for by the formation of lower brominated congeners. Debrominated products detected in the spiked dust included all three nonabrominated congeners (BDE 206, BDE 207, and BDE 208) and several octabrominated congeners (BDE 196, BDE 197, BDE 201, BDE 202, and BDE 203/200). In technical commercial octa‐BDE mixtures, BDE 201 is a very small component (below detection limit to 0.8%), and BDE 202 is not detected. Therefore, the presence of these congeners in house dust may provide a marker of environmental debromination of BDE 209. The ratio of BDE 197 to BDE 201 may also be indicative of BDE 209 degradation. as the ratio of these two congeners appeared to reach a steady‐state value (∼1) in both exposure scenarios in the present study.
•Contaminants of emerging concern were measured in mussels along the California coast.•Sixty-eight total stations. Sixty-seven of the 167 analytes had at least one detect.•The influence of ...urbanization, agriculture, and ocean discharge was investigated.•Alkylphenols, lomefloxacin, and PBDE were the most abundant contaminants.•Perfluorinated compound and HBCD detection frequencies were greater than 25%.
Contaminants of emerging concern were measured in mussels collected along the California coast in 2009–2010. The seven classes were alkylphenols, pharmaceuticals and personal care products, polybrominated diphenyl ethers (PBDE), other flame retardants, current use pesticides, perfluorinated compounds (PFC), and single walled carbon nanotubes. At least one contaminant was detected at 67 of the 68 stations (98%), and 67 of the 167 analytes had at least one detect (40%). Alkylphenol, PBDE, and PFC concentrations increased with urbanization and proximity to storm water discharge; pesticides had higher concentrations at agricultural stations. These results suggest that certain compounds; for example, alkylphenols, lomefloxacin and PBDE, are appropriate for inclusion in future coastal bivalve monitoring efforts based on maximum concentrations >50ng/g dry weight and detection frequencies >50%. Other compounds, for example PFC and hexabromocyclododecane (HBCD), may also be suggested for inclusion due to their >25% detection frequency and potential for biomagnification.
The persistence of trace organic chemicals in treated effluent derived from both centralized wastewater treatment plants (WWTPs) and decentralized wastewater treatment systems (DEWATS) is of concern ...due to their potential impacts on human and ecosystem health. Here, we utilize non-targeted analysis (NTA) with comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC × GC/TOF-MS) to conduct an evaluation of the common persistent and removed compounds found in two centralized WWTPs in the USA and South Africa and one DEWATS in South Africa. Overall, removal efficiencies of chemicals were similar between the treatment plants when they were compared according to the number of chemical features detected in the influents and effluents of each treatment plant. However, the DEWATS treatment train, which has longer solids retention and hydraulic residence times than both of the centralized WWTPs and utilizes primarily anaerobic treatment processes, was able to remove 13 additional compounds and showed a greater decrease in normalized peak areas compared to the centralized WWTPs. Of the 111 common compounds tentatively identified in all three influents, 11 compounds were persistent in all replicates, including 5 compounds not previously reported in effluents of WWTPs or water reuse systems. There were no significant differences among the physico-chemical properties of persistent and removed compounds, but significant differences were observed among some of the molecular descriptors. These results have important implications for the treatment of trace organic chemicals in centralized and decentralized WWTPs and the monitoring of new compounds in WWTP effluent.
•Non-targeted analysis (NTA) identified 111 common WWTP influent compounds.•11 of the common influent compounds were persistent in the studied WWTP effluents.•Anaerobic treatment reduced chemical peak areas more than conventional treatment.•NTA revealed 5 new compounds not previously reported in WWTP effluent.•Physico-chemical properties did not differ among persistent and removed compounds.
Understanding the health implications of human exposure to mixtures of chemical contaminants is aided by analytical methods that can screen for a broad range of both expected and unexpected ...compounds. We performed a proof-of-concept analysis combining human breast milk, a biomonitoring matrix for determining contaminant exposure to mothers and infants, with a non-targeted method based on comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS). A total of 172 presumably anthropogenic halogenated compounds and non-halogenated cyclic and aromatic compounds were tentatively identified in breast milk from San Diego, California through mass spectral database searches. Forty of the compounds were prioritized for confirmation based on halogenation or 100% frequency of detection, and the identities of 30 were verified using authentic standards. Thirty-four (85%) of the prioritized contaminants are not typically monitored in breast milk surveys, and 31 (77%) are regulated in at least one market worldwide, indicating breast milk may be a useful biomonitoring matrix for non-targeted analysis and the assessment of human exposure to future emerging or undiscovered contaminants.
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•Breast milk as a useful biomonitoring matrix for non-targeted analysis.•Successful screening, prioritization, and identification via nontargeted analysis.•172 halogenated and non-halogenated cyclic and aromatic compounds identified in breast milk by non-targeted analysis.•85% of 40 prioritized contaminants are not typically monitored in breast milk surveys.•Among the highly identified compounds through mass spectral similarity, 94% verification success rate achieved.
Despite decades-long bans on the production and use of certain chemicals, many halogenated organic compounds (HOCs) are persistent and can bioaccumulate in the marine environment with the potential ...to cause physiological harm to marine fauna. Highly lipid-rich tissue (e.g., marine mammal blubber) functions as a reservoir for HOCs, and selecting ideal indicator species is a priority for retrospective and proactive screening efforts. We selected five marine mammal species as possible indicators for the Southern California Bight (SCB) and applied a non-targeted analytical method paired with an automated data reduction strategy to catalog a broad range of known, known but unexpected, and unknown compounds in their blubber. A total of 194 HOCs were detected across the study species (n = 25 individuals), 81% of which are not routinely monitored, including 30 halogenated natural products and 45 compounds of unknown structure and origin. The cetacean species (long-beaked common dolphin, short-beaked common dolphin, and Risso's dolphin) averaged 128 HOCs, whereas pinnipeds (California sea lion and Pacific harbor seal) averaged 47 HOCs. We suspect this disparity can be attributed to differences in life history, foraging strategies, and/or enzyme-mediated metabolism. Our results support proposing (1) the long- and short-beaked common dolphin as apex marine predator sentinels for future and retrospective biomonitoring of the SCB ecosystem and (2) the use of non-targeted contaminant analyses to identify and prioritize emerging contaminants. The use of a sentinel marine species together with the non-targeted analytical approach will enable a proactive approach to environmental contaminant monitoring.
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•Organic contaminants were identified in Southern California marine mammal blubber.•Cetaceans accumulated more contaminants than pinnipeds.•Common dolphins are proposed as sentinels for emerging contaminants in this region.
Targeted environmental monitoring reveals contamination by known chemicals, but may exclude potentially pervasive but unknown compounds. Marine mammals are sentinels of persistent and bioaccumulative ...contaminants due to their longevity and high trophic position. Using nontargeted analysis, we constructed a mass spectral library of 327 persistent and bioaccumulative compounds identified in blubber from two ecotypes of common bottlenose dolphins (Tursiops truncatus) sampled in the Southern California Bight. This library of halogenated organic compounds (HOCs) consisted of 180 anthropogenic contaminants, 41 natural products, 4 with mixed sources, 8 with unknown sources, and 94 with partial structural characterization and unknown sources. The abundance of compounds whose structures could not be fully elucidated highlights the prevalence of undiscovered HOCs accumulating in marine food webs. Eighty-six percent of the identified compounds are not currently monitored, including 133 known anthropogenic chemicals. Compounds related to dichlorodiphenyltrichloroethane (DDT) were the most abundant. Natural products were, in some cases, detected at abundances similar to anthropogenic compounds. The profile of naturally occurring HOCs differed between ecotypes, suggesting more abundant offshore sources of these compounds. This nontargeted analytical framework provided a comprehensive list of HOCs that may be characteristic of the region, and its application within monitoring surveys may suggest new chemicals for evaluation.
Analytical methods for contaminant monitoring are generally targeted; i.e., they measure defined lists of compounds. Routine monitoring projects using targeted methods are not usually designed to ...screen for unrecognized or novel contaminants and therefore miss compounds within the region or population of study that cause, or have the potential to cause, adverse biological impacts. We describe a nontargeted analytical method utilizing direct sample introduction coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry. To test the capabilities of this instrumental method within the context of marine contaminant surveys, we characterized a broad array of nonpolar, persistent, and bioaccumulative contaminants in Atlantic common dolphin ( Delphinus delphis ) blubber, including compounds that are not typically monitored. Compound identifications were made by searching a standard reference database, by contemporaneously analyzing mass spectra from reference standards, and by de novo interpretation. We identified a total of 271 compounds belonging to 24 classes; all compounds but 1 were halogenated. Anthropogenic contaminants and halogenated natural products were concurrently detected. A total of 86 compounds were anthropogenic contaminants that are not routinely targeted in environmental surveys, and 54 compounds were halogenated natural products. A total of 112 spectra were identified de novo, demonstrating that exclusive reliance on commercially available reference standards and mass spectral libraries may miss a significant fraction of identifiable compounds. We also cataloged 27 halogenated mass spectra that were not able to be identified. Due to the volume and complexity of the identification data, we developed custom software to organize and provide shared access to the identified mass spectra and related information. The nontargeted analytical method and data reporting system, in combination with the analysis of a high-trophic-level sentinel species, demonstrates a framework for creating an inventory of persistent and bioaccumulative contaminants in marine environments, with the future goal of suggesting new compounds for further investigation by targeted monitoring and risk assessment.
To catalog the diversity and abundance of halogenated organic compounds (HOCs) accumulating in high trophic marine species from the southwestern Atlantic Ocean, tissue from bottlenose dolphins ...(Tursiops truncatus) stranded or incidentally captured along the coast of Rio de Janeiro, Brazil, were analyzed by a nontargeted approach based on GC×GC/TOF-MS. A total of 158 individual HOCs from 32 different structural classes were detected in the blubber of 4 adult male T. truncatus. Nearly 90% of the detected compounds are not routinely monitored in the environment. DDT-related and mirex/dechlorane-related compounds were the most abundant classes of anthropogenic origin. Methoxy-brominated diphenyl ethers (MeO-BDEs) and chlorinated methyl- and dimethyl bipyrroles (MBPs and DMBPs) were the most abundant natural products. Reported for the first time in southwestern Atlantic cetaceans and in contrast to North American marine mammals, chlorinated MBPs and DMBPs were more abundant than their brominated and/or mixed halogenated counterparts. HOC profiles in coastal T. truncatus from Brazil and California revealed a distinct difference, with a higher abundance of MeO-BDEs, mirex/dechloranes and chlorinated bipyrroles in the Brazilian dolphins. Thirty-six percent of the detected HOCs had an unknown structure. These results suggest broad geographical differences in the patterns of bioaccumulative chemicals found in the marine environment and indicate the need to develop more complete catalogs of HOCs from various marine environments.
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