Critical Review of Processing and Classification Techniques for Images and Spectra in Microplastic Research.

Microplastic research is a rapidly developing field, with urgent needs for high throughput and automated analysis techniques. We conducted a review covering image analysis from optical microscopy, scanning electron microscopy, fluorescence microscopy, and spectral analysis from Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, pyrolysis gas-chromatography mass-spectrometry, and energy dispersive X-ray spectroscopy. These techniques were commonly used to collect, process, and interpret data from microplastic samples. This review outlined and critiques current approaches for analysis steps in image processing (color, thresholding, particle quantification), spectral processing (background and baseline subtraction, smoothing and noise reduction, data transformation), image classification (reference libraries, morphology, color, and fluorescence intensity), and spectral classification (reference libraries, matching procedures, and best practices for developing in-house reference tools). We highlighted opportunities to advance microplastic data analysis and interpretation by (i) quantifying colors, shapes, sizes, and surface topologies with image analysis software, (ii) identifying threshold values of particle characteristics in images that distinguish plastic particles from other particles, (iii) advancing spectral processing and classification routines, (iv) creating and sharing robust spectral libraries, (v) conducting double blind and negative controls, (vi) sharing raw data and analysis code, and (vii) leveraging readily available data to develop machine learning classification models. We identified analytical needs that we could fill and developed supplementary information for a reference library of plastic images and spectra, a tutorial for basic image analysis, and a code to download images from peer reviewed literature. Our major findings were that research on microplastics was progressing toward the use of multiple analytical methods and increasingly incorporating chemical classification. We suggest that new and repurposed methods need to be developed for high throughput screening using a diversity of approaches and highlight machine learning as one potential avenue toward this capability.

Regional assessment of persistent organic pollutants in resident mussels from New Jersey and New York estuaries following Hurricane Sandy.

Resident mussels are effective indicators of ecosystem health and have been utilized in national assessment and monitoring studies for over two decades. Mussels were chosen because contaminant concentrations in their tissues respond to changes in ambient environmental levels, accumulation occurs with little metabolic transformation and a substantial amount of historic data were available. Mussels were collected from 10 previously studied locations approximately a year after Hurricane Sandy. Regionally, concentrations of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) decreased significantly, while concentrations of organochlorine pesticides (OCPs) remained unchanged, and polybrominated diphenyl ethers (PBDEs) increased compared to historic concentrations. Although concentrations of PCBs, OCPs and PAHs were at or near record low concentrations, long-term trends did not change after Hurricane Sandy. To effectively measure storm-induced impacts it is necessary to understand the factors influencing changes in mussel body burdens and have a long-term monitoring network and an ability to mobilize post event.

Polychlorinated biphenyls and organochlorine pesticides as intrinsic tracer tags of foraging grounds of bluefin tuna in the northwest Atlantic Ocean.

Researchers have utilized chemical fingerprints in the determination of habitat utilization and movements of the aquatic animals. In the present effort, we analyzed polychlorinated biphenyl (PCB) congeners and organochlorine pesticides in the samples of juvenile bluefin tuna caught offshore of Virginia, and in larger bluefin tuna from the Gulf of Maine and near Nova Scotia. For a given specimen, or a given location, PCB concentrations were highest, followed by DDTs, and chlordanes. Average contaminant concentrations from fish captured from the three locations were not significantly different; and PCBs, DDTs, and chlordanes correlated well with each other. Trans-nonachlor/PCB 153 ratios in bluefin tuna of eastern Atlantic (i.e., Mediterranean) origin are low compared to the corresponding ratios in fish in the western Atlantic. As the former migrate to the western Atlantic, these ratios gradually turnover due to the accumulation of biomass from forage contaminated with higher trans-nonachlor/PCB 153 ratio reflecting dissimilar use of chlordane pesticides on two sides of the Atlantic Ocean. The trans-nonachlor/PCB 153 ratio indicated that one juvenile bluefin tuna from offshore of Virginia and one large bluefin tuna from Gulf of Maine in the present study originated from foraging grounds in the Mediterranean Sea, and that they have made the trans-Atlantic migrations. The remaining individuals were determined to be either spawned in the Gulf of Mexico or the trans-nonachlor/PCB 153 ratio for the putative Mediterranean bluefin tuna was completely turned over to resemble the ratio characteristic to the western Atlantic. Based on the turnover time for trans-nonachlor/PCB 153 ratio previously determined, the residence time of juvenile bluefin tuna offshore Virginia was estimated to be at least 0.8 to 1.6years. A discriminant function analysis (DFA) plot of total PCB normalized signatures of PCB congeners showed three separate clusters, which suggested that bluefin tuna from offshore Virginia, Gulf of Maine, and Nova Scotia could have had extended residences and foraging within the areas of capture to be able to sustain the stable signatures of PCB congeners. The DFA cluster results supported the concept of metapopulation theory of spatial ecology comprising discrete aggregates of local populations of bluefin tuna where the desired prey species are likely to be abundant. Despite their highly migratory trait and endothermic advantage of foraging in broader and colder habitats, the movements and mixing across the aggregation ranges related to feeding did not appear to be extensive. Advancement in the understanding of bluefin tuna population dynamics beyond the coarse concept of trans-Atlantic migrations to the metapopulation hypothesis provides a novel exploratory tool in the stock assessment and resource management. As the chemical tracer tags are fortified naturally and document the time- and space-integrated foraging history, they promise to serve as the low-cost alternatives to the high-cost electronic data recording tags employed for addressing the migratory movements of bluefin tuna. Between the different potential chemical tracer tags, a distinct advantage of PCB/pesticide analysis over the otolith micro-constituent analysis is that the muscle tissue of a given individual bluefin tuna can be sampled repeatedly for PCB/pesticide analysis over different spatial and temporal scales in a non-lethal manner.

Young of the year bluefish (Pomatomus saltatrix) as a bioindicator of estuarine health: Establishing a new baseline for persistent organic pollutants after Hurricane Sandy for selected estuaries in New Jersey and New York.

Atlantic coastal bays of the US are essential habitat for young of year bluefish (Pomatomus saltatrix). Their residence in these estuaries during critical life stages, high lipid content, and piscivory make bluefish an ideal bioindicator species for evaluating estuarine health. Individual whole fish from four estuaries impacted by Hurricane Sandy were collected in August 2013, analyzed for a suite of persistent organic pollutants (POPs) including polychlorinated biphenyls, polybrominated diphenyl ethers and organochlorine pesticides and evaluated using health metrics. Concentrations in whole bluefish differed by estuary; however, concentrations for many POPs decreased or were similar to those observed prior to the hurricane. Prevalence of the ectoparasitic gill isopod (Lironeca ovalis) varied by estuary and no relationships between contaminants and lesions were observed. Bluefish should be considered for monitoring programs and, if sampled frequently, could be an effective bioindicator of incremental and episodic changes in contaminants within aquatic food webs.

Polybrominated diphenyl ether congeners in the young-of-the-year bluefish, Pomatomus saltatrix, from several nursery habitats along the US Atlantic coastline.

Spatial trends of polybrominated diphenyl ether (PBDE) congeners were examined by using high resolution gas chromatography-low resolution electron impact mass spectrometry (GC-EIMS) in 414 samples of young-of-the-year (YOY) bluefish (Pomatomus saltatrix) collected from a total of 29 nursery habitats along the US Atlantic coastline from Massachusetts to Florida. Of the 26 target PBDE congeners, BDE-47 (4 Br), BDE-100 (5 Br), BDE-49 (4 Br), BDE-99 (5 Br), and BDE-154 (6 Br) were the five most frequently detected congeners in the order of decreasing importance. The sum of the concentrations of five major PBDE congeners, referred to as ΣPBDEs, varied between estuaries and also among samples from a given estuary. ΣPBDEs were lowest in YOY bluefish from Vineyard Sound, Nantucket Sound, Great Bay, Delaware Bay, Lynnhaven Bay, Cape Lookout, and Crescent Beach, with maximum ΣPBDE concentrations below 10 ng/g wet weight. ΣPBDEs in three bluefish samples from Stamford Harbor were detected at relatively high to unusually high concentrations of 69.1, 205, and 561 ng/g wet weight. ΣPBDE values for other Stamford Harbor bluefish were generally low. Highest PBDE concentrations were detected in the vicinity of industrial and urban locations within the New York-New Jersey metropolitan complex. Among them, bluefish from Newark Bay were generally the most contaminated with an average ΣPBDE value of 56.6 ± 30.8 ng/g wet weight. ΣPBDEs in bluefish from Newark Bay were numerically greater than ΣPBDEs in bluefish from all locations, however these differences were not statistically significant. Modest to good correlations between ΣPBDEs and lipids were observed for YOY bluefish from Buzzards Bay, Upper New Bedford Harbor, Lower New Bedford Harbor, Outer New Bedford Harbor, Providence Harbor, Housatonic River, Norwalk Harbor, Little Neck Bay, Newark Bay, Sandy Hook Bay, Great Bay, Delaware Bay, Patuxent River and Crescent Beach. Poor correlations between ΣPBDE and lipids were observed for bluefish from other estuaries. ΣPBDEs were not always correlated with fish length or weight. ΣPBDEs in YOY bluefish along the US Atlantic coastline modestly paralleled ΣPBDEs in mussels and oysters, from not exact but geographically loosely similar locations, reported in the NOAA Mussel Watch Program. A number of researchers who used the high resolution mass spectrometry reported additional PBDE congeners. Although PBDE congeners we report do appear to be the prominent congeners in these studies, it is likely that the comparisons will be skewed in certain instances.

Bioaccumulation of polychlorinated biphenyls and organochlorine pesticides in young-of-the-year bluefish (Pomatomus saltatrix) in the vicinity of a Superfund Site in New Bedford Harbor, Massachusetts, and in the adjacent waters.

Spatial gradients of polychlorinated biphenyls (PCBs) and organochlorine pesticides were examined in the young-of-the-year (YOY) bluefish (Pomatomus saltatrix) in the vicinity of a PCB Superfund Site in New Bedford Harbor, Massachusetts, and in the adjacent waters. PCB concentrations in bluefish varied between different locations, and also among fish from a given location. A generally decreasing gradient in PCB concentrations was evident as the bluefish were collected away from the Superfund Site. The average sum of PCB concentrations were highest for bluefish collected in the Upper Harbor between Interstate-195 Bridge and Coggeshall Street Bridge (Upper Harbor), followed by bluefish in Lower Harbor from north of Popes Island Bridge (Lower Harbor), and bluefish from Outer Harbor south of Hurricane Barrier (Outer Harbor). The levels of PCBs in bluefish from Clarks Cove and PCBs in bluefish from Buzzards Bay were similar and lowest among all bluefish specimens analyzed in the present study. Pesticide concentrations were about one order of magnitude or lower than the PCB concentrations, and the gradient of pesticide concentrations generally followed the gradient of PCB concentrations. Some of the commonly detected pesticides in the order of decreasing concentrations included DDTs and metabolites, heptachlor epoxide, endosulfan sulfate, and α-chlordane. Distribution of PCBs and organochlorine pesticides were examined in the tissues of YOY bluefish from Clarks Cove. PCBs and lipids in the brain samples of YOY bluefish were generally numerically greater than PCBs in the liver samples, but these differences were not statistically significant. PCBs and lipids in hypaxial muscle samples were numerically greater than PCBs in epaxial muscle samples, although these two groups of tissues were not statistically different. Despite the higher susceptibility of lighter PCB homologs to geophysical and biogeochemical weathering processes, the relative dominance of lighter homologs in the Upper Harbor and Lower Harbor samples suggested ongoing or recent sources of these lighter PCBs, particularly Aroclor 1242 and Aroclor 1016 in this area. The presence of heavier homologs in the Upper Harbor and Lower Harbor bluefish samples could be attributed to Aroclor 1252 and Aroclor 1254 that were being used in relatively smaller quantities in the manufacture of electrical components in addition to Aroclor 1242 and Aroclor 1016. The concentration of heavier PCB homologs appears to increase in YOY bluefish the further away from the PCB Superfund Site in the Acushnet Estuary the samples were collected. Principal component analyses of PCB 153 normalized concentrations of the individual PCB congeners resulted in two general groupings; a relatively tight group comprised of YOY bluefish from Upper Harbor, Lower Harbor, and Outer Harbor, and a rather loose and more dispersed group comprised of Buzzards Bay bluefish and the tissue samples of bluefish from Clarks Cove. Principal component analyses of major pesticides suggested close groupings of bluefish from Clarks Cove and bluefish from Buzzards Bay. Pesticides in bluefish from Upper Harbor, Lower Harbor, and Outer Harbor formed a loose group, with some bluefish from these locations populating close to Clarks Cove and Buzzards Bay bluefish. Although PCBs have been implicated in various behavioral and health effects in the experimental and field studies, the deleterious effects of chronic exposure to high concentrations of PCBs and the potential for recruitment of New Bedford Harbor YOY bluefish population to the adult stock remains obscure. Adaptive or evolutionary resistance to contaminants have been documented in resident species in some highly contaminated estuaries, however similar responses have not been investigated in the migratory species like bluefish. The results of the present study provide a reference baseline for YOY bluefish for "before-and-after" comparative studies and other toxicological studies for the New Bedford Harbor Superfund Site that is currently being remediated.

Atlantic bluefin tuna (Thunnus thynnus) population dynamics delineated by organochlorine tracers.

Atlantic bluefin tuna (ABFT) are highly valued and heavily exploited, and critical uncertainties regarding their population structure hinder effective management. Evidence supports the existence of two breeding populations of ABFT; a western population in the Gulf of Mexico and an eastern population in the Mediterranean Sea; both of which migrate and mix in the North Atlantic. Conventional tagging studies suggest low rates of trans-Atlantic migrations; however, electronic tagging and stable isotopes in otoliths indicate stock mixing up to 57% between management zones delineated by 45 degrees W longitude. Here we show that organochlorine pesticides and polychlorinated biphenyls (PCBs) can be used as tracers of bluefin tuna foraging grounds in the North Atlantic and confirm that stock mixing of juvenile tuna within the U.S. Mid Atlantic Bight is indeed high (33-83% eastern origin), and is likely spatially and temporally variable. We further demonstrate that >10% of the Mediterranean population is migratory, that young bluefin tuna migrate from the Mediterranean to western Atlantic foraging grounds as early as age 1, and then return to the Mediterranean Sea as young as age 5, presumably to breed. The tracer method described here provides a novel means for distinguishing bluefin tuna populations and ontogenetic shifts in migration in the North Atlantic.