Luke K. Ackerman

Concentration of Bisphenol A in Highly Consumed Canned Foods on the U.S. Market

Metal food and drink cans are commonly coated with epoxy films made from phenolic polymers produced from bisphenol A (BPA). It is well established that residual BPA monomer migrates into can contents during processing and storage. While a number of studies have reported BPA concentrations in foods from foreign markets and specialty foods on the U.S. market, very few peer-reviewed data for the BPA concentrations in canned food from the U.S. market were available. This study quantified BPA concentrations in 78 canned and two frozen food products from the U.S. market using an adaptation of a previously reported liquid chromatography-tandem mass spectrometry method. The tested products represented 16 different food types that are from the can food classifications that constitute approximately 65% of U.S. canned food sales and canned food consumption. BPA was detected in 71 of the 78 canned food samples but was not detected in either of the two frozen food samples. Detectable BPA concentrations across all foods ranged from 2.6 to 730 ng/g. Large variations in BPA concentrations were found between different products of the same food type and between different lots of the same product. Given the large concentration ranges, the only distinguishable trend was that fruits and tuna showed the lowest BPA concentrations. Experiments with fortified frozen vegetables and brine solutions, as well as higher BPA concentrations in canned food solids over liquid portions, clearly indicated that BPA partitions into the solid portion of foods.

Assessing direct analysis in real-time-mass spectrometry (DART-MS) for the rapid identification of additives in food packaging.

The ambient ionization technique direct analysis in real time (DART) was characterized and evaluated for the screening of food packaging for the presence of packaging additives using a benchtop mass spectrometer (MS). Approximate optimum conditions were determined for 13 common food-packaging additives, including plasticizers, anti-oxidants, colorants, grease-proofers, and ultraviolet light stabilizers. Method sensitivity and linearity were evaluated using solutions and characterized polymer samples. Additionally, the response of a model additive (di-ethyl-hexyl-phthalate) was examined across a range of sample positions, DART, and MS conditions (temperature, voltage and helium flow). Under optimal conditions, molecular ion (M+H+) was the major ion for most additives. Additive responses were highly sensitive to sample and DART source orientation, as well as to DART flow rates, temperatures, and MS inlet voltages, respectively. DART-MS response was neither consistently linear nor quantitative in this setting, and sensitivity varied by additive. All additives studied were rapidly identified in multiple food-packaging materials by DART-MS/MS, suggesting this technique can be used to screen food packaging rapidly. However, method sensitivity and quantitation requires further study and improvement.

Determination of Bisphenol A in U.S. Infant Formulas: Updated Methods and Concentrations

An updated survey of U.S. infant formula was conducted to determine the concentrations of bisphenol A (BPA). The purpose was to accurately assess BPA concentrations across the infant formula market, accounting for lot variability, and determine if geographic location or can age influences BPA concentrations. A method was developed to measure BPA in formula utilizing isotope dilution, solid-phase extraction, and liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The method was tested and found to be reproducible (10% relative standard deviation), reliable (47 +/- 1% recovery), and sensitive (0.15 ng g(-1) method detection limit). Over 160 analyses were conducted using 104 formula containers representing 36 products. Samples from U.S. east and west coast markets demonstrated no significant difference, and concentrations in older cans were not higher. BPA concentrations in liquid formula (0.48-11 ng g(-1)) were consistent with previous studies, and BPA was detected in only 1 of 14 powder formula products analyzed.

The Western Airborne Contaminant Assessment Project (WACAP): An Interdisciplinary Evaluation of the Impacts of Airborne Contaminants in Western U.S. National Parks

The National Park Service Organic Act of 1916 (1) required protection of the national parks for perpetuity by tasking the National Park Service (NPS) to maintain these lands “...unimpaired for the enjoyment of future generations.” Near the close of the last century, the NPS became aware of a new body of research describing a potential ecosystem threat that could not be ignored. Toxic airborne contaminants were increasingly being found in the world’s most pristine alpine and polar ecosystems, far from where such chemicals were produced or used, and the risks to the national parks of the western U.S. were unknown. Airborne contaminants present a broad range of potential risks to these ecosystems, largely due to bioaccumulation and or biomagnification of toxicants in biota, particularly vertebrates, that can result in loss of fecundity, unfit offspring, maladaptive behavior, and even death. As an outgrowth of these concerns, the Western Airborne Contaminants Assessment Project (WACAP) was initiated in 2002 to determine the risk from airborne contaminants to ecosystems and food webs in national parks of the U.S. The specific objectives that guided design and implementation of WACAP were the following: 1. Determine if contaminants were present in western national parks. 2. If contaminants were present, determine in what way and where they were accumulating (geographically and by elevation). EP A Environ. Sci. Technol. 2010, 44, 855–859

Ambient Ionization–Accurate Mass Spectrometry (AMI-AMS) for the Identification of Nonvisible Set-off in Food-Contact Materials

Set-off is the unintentional transfer of substances used in printing from the external printed surface of food packaging to the inner, food-contact surface. Ambient ionization-accurate mass spectrometry (AMI-AMS) detected and identified compounds from print set-off not visible to the human eye. AMI mass spectra from inner and outer surfaces of printed and nonprinted food packaging were compared to detect and identify nonvisible set-off components. A protocol to identify unknowns was developed using a custom open-source database of printing inks and food-packaging compounds. The protocol matched print-related food-contact surface ions with the molecular formulas of common ions, isotopes, and fragments of compounds from the database. AMI-AMS was able to detect print set-off and identify seven different compounds. Set-off on the packaging samples was confirmed using gas chromatographic-mass spectrometric (GC-MS) analysis of single-sided solvent extracts. N-Ethyl-2(and 4)-methylbenzenesulfonamide, 2,4-diphenyl-4-methyl-1(and 2)-pentene, and 2,4,7,9-tetramethyl-5-decyne-4,7-diol were present on the food-contact layer at concentrations from 0.21 to 2.7 ± 1.6 μg dm⁻², corresponding to nearly milligram per kilogram concentrations in the packaged food. Other minor set-off compounds were detected only by AMI-AMS, a fast, simple, and thorough technique to detect and identify set-off in food packaging.

Non-visible print set-off of photoinitiators in food packaging: detection by ambient ionisation mass spectrometry

Direct analysis in real time coupled to time-of-flight mass spectrometry (DART/TOF-MS) was used to detect the non-visible set-off of photoinitiators on the food contact surface of three different packages. The samples were intentionally under-cured to provoke set-off. Twelve commercially available photoinitiators were included in the ink formulations including α-amino-, morpholino, and α-hydroxy benzophenones, thioxanthones, aryl-phosphine oxide and three polymeric versions of these. Major colours of the packages’ prints were analysed, as well as the specific areas of the inner surface in contact with them. Larger quantities of photoinitiators were detected on the food contact areas in contact with the darker colours of the images. Speed-cure 7005 and 4-phenylbenzophenone were the compounds most susceptible to set-off in each of the samples by DART response. An identification protocol for unknown set-off compounds was tested, resulting in the set-off detection of diethylene glycol ethers, erucamide and acrylates, and confirmed by solvent extraction GC-MS analysis. Finally, DART/TOF-MS was scanned across transects of the food contact side of packages to map the presence of photoinitiators. Higher photoinitiator signals were observed in patterns corresponding to the printed image, suggesting DART/TOF-MS might “image” print set-off.

Reproductive Abnormalities in Trout from Western U.S. National Parks

Abstract Reproductive disruption is well documented in polluted areas, such as below sewage treatment plants, but not in ecologically protected environments, such as national parks. In a majority of subalpine lakes sampled in Rocky Mountain and Glacier National parks, we observed intersex male cutthroat trout Oncorhynchus clarkii and brook trout Salvelinus fontinalis at frequencies of 9-33%. Intersexuality, one form of reproductive disruption, is the presence of both male and female reproductive structures in the same animal. Male cutthroat trout, rainbow trout O. mykiss, and brook trout from these parks also produced elevated levels of the estrogen-responsive protein vitellogenin, another indicator of reproductive disruption. We did not find reproductive abnormalities in national parks of the Sierra Nevada, Cascades, Olympics, Brooks, or Alaska ranges. To determine whether gonad abnormalities were evident in mountain ecosystems before the production of organic pollutants, we sampled various species of th...

Humidity Affects Relative Ion Abundance in Direct Analysis in Real Time Mass Spectrometry of Hexamethylene Triperoxide Diamine

Unstable explosive hexamethylene triperoxide diamine (HMTD) is dangerous in quantity and benefits from the minimal sampling handling associated with atmospheric pressure chemical ionization for mass spectral analysis. Seasonal variation observed in HMTD mass spectra suggested a humidity dependence. Therefore, direct analysis in real time (DART) ionization mass spectra were acquired at a range of humidity values. An enclosure was designed to fit around the ion source and mass spectrometer inlet at atmospheric pressure. The enclosure was supplied with controlled amounts of humidified air from a test atmosphere generator to create programmable conditions for ambient analysis. The relative abundance and fragmentation of analyte ions were observed to change reliably with changing humidity values and, to a lesser degree, temperature. Humidity at such plasma-based ion sources should be regulated to avoid ∼90% shifts in relative ion abundance and provide stability and reproducibility of HMTD analysis.

Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources

AbstractPost-plasma ambient desorption/ionization (ADI) sources are fundamentally dependent on surrounding water vapor to produce protonated analyte ions. There are two reports of humidity effects on ADI spectra. However, it is unclear whether humidity will affect all ADI sources and analytes, and by what mechanism humidity affects spectra. Flowing atmospheric pressure afterglow (FAPA) ionization and direct analysis in real time (DART) mass spectra of various surface-deposited and gas-phase analytes were acquired at ambient temperature and pressure across a range of observed humidity values. A controlled humidity enclosure around the ion source and mass spectrometer inlet was used to create programmed humidity and temperatures. The relative abundance and fragmentation of molecular adduct ions for several compounds consistently varied with changing ambient humidity and also were controlled with the humidity enclosure. For several compounds, increasing humidity decreased protonated molecule and other molecular adduct ion fragmentation in both FAPA and DART spectra. For others, humidity increased fragment ion ratios. The effects of humidity on molecular adduct ion fragmentation were caused by changes in the relative abundances of different reagent protonated water clusters and, thus, a change in the average difference in proton affinity between an analyte and the population of water clusters. Control of humidity in ambient post-plasma ion sources is needed to create spectral stability and reproducibility. Graphical Abstractᅟ

Sources and fate of chiral organochlorine pesticides in western U.S. National Park ecosystems

The enantiomer fractions (EFs) of alpha-hexachlorocyclohexane (α-HCH), cis-, trans-, and oxychlordane, and heptachlor epoxide were measured in 73 snow, fish, and sediment samples collected from remote lake catchments, over a wide range of latitudes, in seven western U.S. National Parks/Preserves to investigate their sources, fate, accumulation and biotransformation in these ecosystems. The present study is novel because these lakes had no inflow or outflow, and the measurement of chiral organochlorine pesticides (OCPs) EFs in snowpack from these lake catchments provided a better understanding of the OCP sources in the western United States, whereas their measurement in fish and sediment provided a better understanding of their biotic transformations within the lake catchments. Nonracemic α-HCH was measured in seasonal snowpack collected from continental U.S. National Parks, and racemic α-HCH was measured in seasonal snowpack collected from the Alaskan parks, suggesting the influence of regional sources to the continental U.S. parks and long-range sources to the Alaskan parks. The α-HCH EFs measured in trout collected from the lake catchments were similar to the α-HCH EFs measured in seasonal snowpack collected from the same lake catchments, suggesting that these fish did not biotransform α-HCH enantioselectively. Racemic cis-chlordane was measured in seasonal snowpack and sediment collected from Sequoia, indicating that it had not undergone significant enantioselective biotransformation in urban soils since its use as a termiticide in the surrounding urban areas. However, nonracemic cis-chlordane was measured in seasonal snowpack and sediments from the Rocky Mountains, suggesting that cis-chlordane does undergo enantioselective biotransformation in agricultural soils. The trout from these lakes showed preferential biotransformation of the (+)-enantiomer of cis-chlordane and the (-)-enantiomer of trans-chlordane.