ABSTRACT
Identifying the sources and fate of microplastics in natural systems has garnered a great deal of attention because of their implications for ecosystem health. This work characterizes the size fraction, morphology, color, and polymer composition of microplastics in western Lake Superior and its adjacent harbor sampled in August and September 2021. The results reveal that the overall microplastic counts are similar, with the harbor stations ranging from 0.62 to 3.32 microplastics per liter and the lake stations ranged from 0.83 to 1.4 microplastics per liter. However, meaningful differences between the sample locations can be seen in the size fraction trends and polymer composition. Namely, the harbor samples had relatively larger amounts of the largest size fraction and more diversity of polymer types, which can be attributed to the urbanized activity and shorter water residence time. Power law size distribution modeling reveals deviations that help in the understanding of potential sources and removal mechanisms, although it significantly underpredicts microplastic counts for smaller-sized particles (5-45 µm), as determined by comparison with concurrently collected microplastic samples enumerated by Nile Red staining and flow cytometry.
Subject(s)
Environmental Monitoring , Estuaries , Lakes , Microplastics , Microplastics/analysis , Lakes/chemistry , Water Pollutants, Chemical/analysisABSTRACT
While plastic pollution in marine and freshwater systems is an active area of research, there is not yet an in-depth understanding of the distributions, chemical compositions, and fates of plastics in aquatic environments. In this study, the magnitude, distribution, and common polymers of microplastic pollution in surface waters in western Lake Superior are determined. Analytical methodology, including estimates of ambient contamination during sample collection and processing, are described and employed. Microscopy, pyrolysis-gas chromatography/mass spectrometry (Pyr-GC/MS), and Fourier transform infrared spectroscopy (FTIR) were used to quantify and identify microplastic particles. In surface waters, fibers were the most frequently observed morphology, and, based upon PyGC/MS analysis, polyvinyl chloride was the most frequently observed polymer, followed by polypropylene and polyethylene. The most common polymer identified by FTIR was polyethylene. Despite the low human population in Lake Superior's watershed, microplastic particles (particularly fibers, fragments, and films) were identified in western-lake surface waters at levels comparable to average values reported in studies within Lake Michigan, the North Atlantic Ocean, and the South Pacific Ocean. This study provides insight into the magnitude of microplastic pollution in western Lake Superior, and describes in detail methodology to improve future microplastics studies in aquatic systems.
Subject(s)
Lakes , Water Pollutants, Chemical , Atlantic Ocean , Environmental Monitoring , Michigan , Microscopy , Pacific Ocean , Plastics , Spectroscopy, Fourier Transform InfraredABSTRACT
Microplastic pollution (plastic particles < 5 mm) has potentially harmful impacts on aquatic ecosystems. Understanding the factors that impact microplastic loading and distribution within aquatic ecosystems is crucial for assessing potential threats from microplastics. Here we examine the extent of microplastic pollution in the surface waters and sediments of four small inland lakes in Minnesota, USA that represent a range of human impacts as well as a variety of watershed and lake characteristics. Surface water particulates and benthic sediments were collected in the summers of 2019 and 2020 to examine the loading of microplastics into these lakes and their distribution throughout the ecosystems. Lower size cut offs were set at 330 µm for surface water particulate samples and 250 µm for sediment samples. Watershed to surface area ratio (WS:SA) and urban development were the most influential factors on microplastic loading. Surface water microplastic concentrations ranged from 27,000 microplastics km-2 in Elk Lake (small WS:SA and minimally developed) to 152,000 microplastics km-2 in White Iron Lake (large WS:SA and low development). Concentrations in benthic sediments ranged from 30 microplastics kg-1 dry sediment in White Iron Lake (forested watershed) to 270 microplastics kg-1 dry sediment in Peltier Lake (urbanized watershed) and were not directly correlated to surface water concentrations. Results from this study highlight the characteristics of small lakes that influence spatial and temporal variability in microplastic loading, retention, and deposition of microplastics to sediments. Further, this study demonstrates the difficulties of accurately predicting microplastic loading and the importance of comprehensive sampling to account for the variability of microplastic loading and distribution in smaller inland lakes.
Subject(s)
Microplastics , Water Pollutants, Chemical , Humans , Plastics , Lakes , Ecosystem , Minnesota , Water Pollutants, Chemical/analysis , Environmental Monitoring , Geologic Sediments , WaterABSTRACT
Quality assurance and quality control (QA/QC) techniques are critical to analytical chemistry, and thus the analysis of microplastics. Procedural blanks are a key component of QA/QC for quantifying and characterizing background contamination. Although procedural blanks are becoming increasingly common in microplastics research, how researchers acquire a blank and report and/or use blank contamination data varies. Here, we use the results of laboratory procedural blanks from a method evaluation study to inform QA/QC procedures for microplastics quantification and characterization. Suspected microplastic contamination in the procedural blanks, collected by 12 participating laboratories, had between 7 and 511 particles, with a mean of 80 particles per sample (±SD 134). The most common color and morphology reported were black fibers, and the most common size fraction reported was 20-212 µm. The lack of even smaller particles is likely due to limits of detection versus lack of contamination, as very few labs reported particles <20 µm. Participating labs used a range of QA/QC techniques, including air filtration, filtered water, and working in contained/'enclosed' environments. Our analyses showed that these procedures did not significantly affect blank contamination. To inform blank subtraction, several subtraction methods were tested. No clear pattern based on total recovery was observed. Despite our results, we recommend commonly accepted procedures such as thorough training and cleaning procedures, air filtration, filtered water (e.g., MilliQ, deionized or reverse osmosis), non-synthetic clothing policies and 'enclosed' air flow systems (e.g., clean cabinet). We also recommend blank subtracting by a combination of particle characteristics (color, morphology and size fraction), as it likely provides final microplastic particle characteristics that are most representative of the sample. Further work should be done to assess other QA/QC parameters, such as the use of other types of blanks (e.g., field blanks, matrix blanks) and limits of detection and quantification.
Subject(s)
Microplastics , Water Pollutants, Chemical , Plastics/analysis , Laboratories , Quality Control , Water/analysis , Environmental Monitoring/methods , Water Pollutants, Chemical/analysisABSTRACT
Previous studies have evaluated method performance for quantifying and characterizing microplastics in clean water, but little is known about the efficacy of procedures used to extract microplastics from complex matrices. Here we provided 15 laboratories with samples representing four matrices (i.e., drinking water, fish tissue, sediment, and surface water) each spiked with a known number of microplastic particles spanning a variety of polymers, morphologies, colors, and sizes. Percent recovery (i.e., accuracy) in complex matrices was particle size dependent, with â¼60-70% recovery for particles >212 µm, but as little as 2% recovery for particles <20 µm. Extraction from sediment was most problematic, with recoveries reduced by at least one-third relative to drinking water. Though accuracy was low, the extraction procedures had no observed effect on precision or chemical identification using spectroscopy. Extraction procedures greatly increased sample processing times for all matrices with the extraction of sediment, tissue, and surface water taking approximately 16, 9, and 4 times longer than drinking water, respectively. Overall, our findings indicate that increasing accuracy and reducing sample processing times present the greatest opportunities for method improvement rather than particle identification and characterization.
Subject(s)
Drinking Water , Water Pollutants, Chemical , Animals , Microplastics , Plastics , Water Pollutants, Chemical/analysis , Environmental MonitoringABSTRACT
Applying two-dimensional correlation spectroscopy to (13)C NMR and FTIR spectra of the high molecular-weight dissolved organic matter (HMW-DOM) isolated along an Elizabeth River/Chesapeake Bay salinity transect shows that HMW-DOM consists of three major components that have different biogeochemical reactivities. The first appears to be a heteropolysaccharide (HPS) component and its contribution to carbon increases as we approach the marine offshore. The second appears to be composed of carboxyl-rich compounds (CRC); its carbon percentage decreases. The third component contains the major functional group of amide/amino sugar (AMS) and its carbon percentage stays almost constant along the salinity transect. It seems that the HPS and CRC are present in many aquatic environments at different relative ratios. The 2D-correlation maps reveal that each of these components is composed of dynamic mixtures of compounds that share similar backbone structures but have significant functional group differences. Two-dimensional (2D) correlation spectroscopy is a powerful new biogeochemical tool to track the changes in complex organic matter as a function of space, time, or environmental effects.
Subject(s)
Carbon/chemistry , Fresh Water/chemistry , Magnetic Resonance Spectroscopy , Spectroscopy, Fourier Transform Infrared , Carbon Isotopes , Cities , SalinityABSTRACT
The abundance of microplastics in natural systems is a concern even in relatively pristine areas such as Lake Superior, on the border between the United States and Canada. In this study, beach sand and surface water were sampled in the Apostle Islands National Lakeshore (APIS) in May and July 2018. Additional sand samples were collected at non-APIS beaches in western Lake Superior in May 2018. Microlitter particles (<4 mm), consisting of microplastics and other low-density particles, were enumerated. Microplastics in sand samples, as identified by melt test, exhibited low abundances (0 to 55 particles/kg dry weight) and were mainly fibers. Microplastics in water samples were also low in abundance (9000 to 40,000 particles/km2) and were mostly fibers. Pyrolysis gas chromatography (pyGCMS) analysis was performed on a subset of microplastics from the sand and water samples. All particles with identifiable mass spectra were polyethylene. When beach sands were processed by density fractionation and filtration, the resulting microlitter samples also contained 260 to 2630 non-plastic particles per kg dry weight. A subset of these non-melting particles was analyzed by Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM/EDS). Results indicated that both organic and inorganic particles were included within non-plastic microlitter. Re-analysis of additional aliquots of the same sand samples using oxidation in addition to density fractionation reduced the number of non-plastic particles by roughly half, further highlighting that many of these were organic. Post-oxidation surface-water microlitter (333 µm to 4 mm) also contained non-plastic low-density particles, which comprised 29 to 47% of the total microlitter particle counts. Based upon color distributions, non-plastic microlitter particles in sand and water samples include a small portion of particles identifiable as anthropogenic. The sources for many microlitter particles cannot be distinguished at present and may be natural in origin.
ABSTRACT
Correction for 'Dissolved organic matter in Lake Superior: insights into the effects of extraction methods on chemical composition' by Hongyu Li et al., Environ. Sci.: Processes Impacts, 2015, 17, 1829-1840.
ABSTRACT
Climate change is expected to profoundly affect the Great Lakes region of North America. An increase in intensity and frequency of rain events is anticipated to deliver more runoff and to increase riverine inputs to Lake Superior's ecosystem. The effects of these changes on key biogeochemical parameters were analyzed by coupling satellite data, water column sensor profiles, and discrete surface-water sampling after two "500-year" flood events in the Lake Superior basin. This study provides both a spatial and a temporal sense of how plumes interacted within the ecosystem. We also determined the significant differences in water quality parameters for plume versus non-plume waters. These two plumes were important for delivery of nutrients, with variable transport of sediments and colored dissolved organic matter (CDOM). Data from the 2012 storm event showed a significant input of total nitrogen (TN), total phosphorous (TP) and CDOM to the system. In the 2016 storm event, carbon cycling parameters (acidity, total inorganic carbon (TIC), and dissolved organic carbon (DOC), and ammonia levels were elevated within the plume. In neither storm event was there a significant difference in chlorophyll a between plume and non-plume waters during our sampling cruises. These two plume events were similar in amount of precipitation, but their effect on the biogeochemistry of Lake Superior varied due to differences in the watersheds where the rain fell. The studied plume events were dynamic, changing with currents, winds and the settling of suspended sediments.
ABSTRACT
Fish ingestion of microplastic has been widely documented throughout freshwater, marine, and estuarine species. While numerous studies have quantified and characterized microplastic particles, analytical methods for polymer identification are limited. This study investigated the applicability of pyr-GC/MS for polymer identification of microplastics extracted from the stomach content of marine fish from the Texas Gulf Coast. A total of 43 microplastic particles were analyzed, inclusive of 30 fibers, 3 fragments, and 10 spheres. Polyvinyl chloride (PVC) and polyethylene terephthalate (PET) were the most commonly identified polymers (44.1%), followed by nylon (9.3%), silicone (2.3%), and epoxy resin (2.3%). Approximately 42% of samples could not be classified into a specific polymer class, due to a limited formation of pyrolytic products, low product abundance, or a lack of comparative standards. Diethyl phthalate, a known plasticizer, was found in 16.3% of the total sample, including PVC (14.3%), silicone (14.3%), nylon (14.3%), and sample unknowns (57.2%).
Subject(s)
Fishes/metabolism , Gastrointestinal Contents/chemistry , Plastics/analysis , Water Pollutants, Chemical/analysis , Animals , Environmental Monitoring/methods , Gas Chromatography-Mass Spectrometry , Plasticizers/analysis , Plasticizers/metabolism , Plastics/metabolism , Seafood/analysis , Stomach/chemistry , Texas , Water Pollutants, Chemical/metabolismABSTRACT
Flooding is a major disturbance that impacts aquatic ecosystems and the ecosystem services that they provide. Predicted increases in global flood risk due to land use change and water cycle intensification will likely only increase the frequency and severity of these impacts. Extreme flooding events can cause loss of life and significant destruction to property and infrastructure, effects that are easily recognized and frequently reported in the media. However, flooding also has many other effects on people through freshwater aquatic ecosystem services, which often go unrecognized because they are less evident and can be difficult to evaluate. Here, we identify the effects that small magnitude frequently occurring floods (< 10-year recurrence interval) and extreme floods (> 100-year recurrence interval) have on ten aquatic ecosystem services through a systematic literature review. We focused on ecosystem services considered by the Millennium Ecosystem Assessment including: (1) supporting services (primary production, soil formation), (2) regulating services (water regulation, water quality, disease regulation, climate regulation), (3) provisioning services (drinking water, food supply), and (4) cultural services (aesthetic value, recreation and tourism). The literature search resulted in 117 studies and each of the ten ecosystem services was represented by an average of 12 ± 4 studies. Extreme floods resulted in losses in almost every ecosystem service considered in this study. However, small floods had neutral or positive effects on half of the ecosystem services we considered. For example, small floods led to increases in primary production, water regulation, and recreation and tourism. Decision-making that preserves small floods while reducing the impacts of extreme floods can increase ecosystem service provision and minimize losses.
ABSTRACT
In the Anthropocene1, watershed chemical transport is increasingly dominated by novel combinations elements, which are hydrologically linked together as 'chemical cocktails.' Chemical cocktails are novel because human activities greatly enhance elemental concentrations and their probability for biogeochemical interactions and shared transport along hydrologic flowpaths. A new chemical cocktail approach advances our ability to: trace contaminant mixtures in watersheds, develop chemical proxies with high-resolution sensor data, and manage multiple water quality problems. We explore the following questions: (1) Can we classify elemental transport in watersheds as chemical cocktails using a new approach? (2) What is the role of climate and land use in enhancing the formation and transport of chemical cocktails in watersheds? To address these questions, we first analyze trends in concentrations of carbon, nutrients, metals, and salts in fresh waters over 100 years. Next, we explore how climate and land use enhance the probability of formation of chemical cocktails of carbon, nutrients, metals, and salts. Ultimately, we classify transport of chemical cocktails based on solubility, mobility, reactivity, and dominant phases: (1) sieved chemical cocktails (e.g., particulate forms of nutrients, metals and organic matter); (2) filtered chemical cocktails (e.g., dissolved organic matter and associated metal complexes); (3) chromatographic chemical cocktails (e.g., ions eluted from soil exchange sites); and (4) reactive chemical cocktails (e.g., limiting nutrients and redox sensitive elements). Typically, contaminants are regulated and managed one element at a time, even though combinations of elements interact to influence many water-quality problems such as toxicity to life, eutrophication, infrastructure and water treatment. A chemical cocktail approach significantly expands evaluations of water-quality signatures and impacts beyond single elements to mixtures. High-frequency sensor data (pH, specific conductance, turbidity, etc.) can serve as proxies for chemical cocktails and improve real-time analyses of water-quality violations, identify regulatory needs, and track water quality recovery following and extreme climate events. Ultimately, a watershed chemical cocktail approach is necessary for effectively co-managing groups of contaminants and provides a more holistic approach for studying, monitoring, and managing water quality in the Anthropocene.
ABSTRACT
Dissolved organic matter (DOM) in aquatic systems plays many biogeochemical roles, acting as a sunscreen, a food source, a trace metal chelator, and a photosensitizer. The efficiency of DOM in these roles is, in part, a function of its composition, which is difficult to determine due to its heterogeneity and the difficulty in isolating representative portions for subsequent molecular level analyses. In this study, the performance of two major types of solid phase extraction (SPE) resins (C18 vs. polymeric SDVB) in disk format (C18 disk vs. SDB-XC disk) was studied using DOM from Lake Superior, the earth's largest lake by area. The performance of the two SPE disks and their influences on the molecular chemical composition of the extracted retentates were studied with UV-vis spectrometry and negative-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). We found that SDB-XC disks outperformed C18 disks in the isolation of DOM in terms of both higher recovery and less fractionation relative to the initial DOM composition. Extracts of the same samples obtained with the different resins shared 70% of molecular formulae. Compounds exclusive to the SDB-XC extractions exhibited similar compound distributions to those of the shared formulae but were enriched in N, P, and S and more aromatic. The C18 exclusive compounds had somewhat higher H/C ratios and contained a large proportion of compounds with oxygen and nitrogen (CHON). Cluster analysis and principle component analysis confirmed that sample location was the main driver of the composition of extracted samples but showed some fractionation of the samples based upon the type of resin.
Subject(s)
Environmental Monitoring/methods , Humic Substances/analysis , Water Pollutants/analysis , Great Lakes Region , LakesABSTRACT
Natural dissolved organic matter (DOM) in aquatic systems plays many environmental roles: providing building blocks and energy for aquatic biota, acting as a sunscreen in surface water, and interacting with anthropogenic compounds to affect their ultimate fate in the environment. Such interactions are a function of DOM composition, which is difficult to ascertain due to its heterogeneity and the co-occurring matrix effects in most aquatic samples. This review focuses on current approaches to the chemical structural characterization of DOM, ranging from those applicable to bulk samples and in situ analyses (UV-visible spectrophotometry and fluorescence spectroscopy) through the concentration/isolation of DOM followed by the application of one or more analytical techniques, to the detailed separation and analysis of individual compounds or compound classes. Also provided is a brief overview of the main techniques used to characterize isolated DOM: mass spectrometry (MS), nuclear magnetic resonance mass spectrometry (NMR) and Fourier transform infrared spectroscopy (FTIR).