Introduction

Particulate Matter (PM) is comprised of both organic (Particulate Organic Matter -- POM) and inorganic components and is an essential part of carbon transport in estuarine environments. Estuaries facilitate and regulate the transport of PM, as well as dissolved carbon, from rivers into the oceans (Fisher et al. 1998; Loh et al. 2006) and produce PM in situ (Savoye et al. 2011; Middelburg and Herman 2007). The dynamic conditions of estuaries create gradients in the abundance and composition of particles, which vary over spans of hours, seasons, or years (Canuel and Zimmerman 1999) and between locations (Fisher et al. 1998). The concentration, size distribution, and dynamics (including aggregation and disaggregation) of PM in estuaries is affected by factors including turbulence, differential settling, Brownian motion, salinity gradients, and compounds produced by organisms that cause particles to aggregate (Eisma et al. 1991). High collision frequency, which depends on the concentration of particles and the energy of the water, can lead to particle aggregation, while turbulence breaks up particles (Fugate and Friedrichs 2003). Near the surface, particle size may be limited by low collision frequency (Fugate and Friedrichs 2003). Aggregation and breakup together drive particle size distributions to an equilibrium distribution, which can vary regionally in response to variation in turbulence and other factors (Chen et al. 1994). Sinking speed also affects particle size distributions, with denser faster sinking particles leaving the pycnocline more quickly than less dense slowly sinking or non-sinking particles (Fugate and Friedrichs 2003). PM that reaches the lower water column of estuaries settles into the bed, where strong turbulence may cause re-suspension of large particles and more breakup (Hill et al. 2001).The Chesapeake Bay is the largest estuary in the United States, with the main stem measuring 320 km (Schubel and Pritchard, 1986). Within the Bay, there are strong salinity gradients, with a low salinity region (< 0.5 ppt) in the northern section, a mesohaline zone (0.5 – 25 ppt) extending approximately from 39˚N latitude to the mouth of the Potomac River, and a high salinity region (> 25 ppt) near the mouth of the Bay (Maryland Department of the Environment). The Chesapeake Bay has an expanding region of seasonal anoxia (Testa 2018; Kemp 1992), with deficits occurring annually in the mesohaline region (Officer et al. 1984). Deoxygenation is driven by microbes at depth consuming the organic portion of particles that originate in high production surface waters (Robinson 2019). In the Chesapeake Bay, these particles originate from surface waters primarily in the mainstem of the Bay (Wang and Hood 2021).  Anoxic regions are intensified by sewage and agricultural runoff, which increase the rate of phytoplankton production (Canuel and Zimmerman 1999). Since the Chesapeake Bay is a region of high biological productivity and diverse habitats, there is high variability in the origin and distribution of PM. In the upper Bay, freshwater input mostly from the Susquehanna River, which deposits nearly one million tons of sediment into the bay annually (Donoghue et al. 1989), accounts for 83% of suspended particles, and shore erosion contributes 13% (Biggs 1969). In the middle Bay, 52% of particles are formed from shore erosion, and 40% come from phytoplankton, both through primary production and the production of skeletal material (Biggs 1969). In the southern Bay, most particulate matter originates in that location from the production and material of phytoplankton and zooplankton. The study of the southern Bay did not find significant contribution by or variation between the mouths of rivers (Canuel and Zimmerman 1999). Particles in the Bay are also affected by resuspension of bottom sediments. Bay topography and the composition of the Bay floor interact to cause regionally variable patterns in sediment resuspension (Xiong et al. 2021).  Turbidity driven by resuspension of particles attenuates light in the northern Bay, which shifts more primary production down toward the central Bay (Moriarty et al. 2020). Resuspension in the central Bay further increases the concentration of organic matter in this region, leading to more remineralization and a decrease in oxygen near the bottom of the water column (Moriarty et al. 2020).The balance of aggregation, disaggregation, and particle transport differ between the mouth of the Bay, the seasonally anoxic mesohaline, and the Upper Bay. Several studies have characterized particle size distributions near the mouth of the Bay: One of these studies combined acoustic and optical measurements of particle properties and identified temporal variability in the sinking speed and size properties of particles near the mouth of the Bay (Fugate and Friedrichs 2002). In another site in the lower Bay, it was found that higher turbulent kinetic energy near the bed is associated with larger particle sizes (Fugate and Friedrichs 2003). This result contrasted with other estuarine river environments in this study, where turbulence near the riverbed fragments particles, keeping their sizes small. The authors suggested that the Chesapeake Bay has a biologically active benthic community, which produce compounds that create large aggregate particles under turbulent conditions (Fugate and Friedrichs 2003).  Furthermore, particle residence time, the amount of time that a particle remains in the water column before remineralizing or becoming incorporated into the sediment also varies across space and time (Xiong and Shen 2022).No study, to our knowledge, has characterized the particle size distribution spectrum in the mesohaline region of the Bay. However, several studies have explored the origin of particles contributing to the seasonally anoxic region of the Bay. Particle transport into the mesohaline is driven in large part by advection of deep water from the high salinity mouth of the Bay and particle sinking (Jonas 1992). Particle tracking experiments have shown that particles that ultimately sink into the anoxic region of the Bay vary in their origin depending on the tidal cycles and corresponding currents (Wang and Hood 2021). The organic portion of this particulate matter has been shown to degrade quickly (Jonas and Tuttle 1990), and so fuels the oxygen removal in this anoxic region.            In the Upper Bay, there is a defined estuarine turbidity maximum (ETM) region, where the Susquehanna River meets the more brackish waters of the main Bay (Schubel and Biggs 1969). The ETM is caused by suspension and entrainment of sediment from the bay floor, which is maintained by interactions between tidal forces and the steep salinity gradient (Sanford et al. 2001). This region is characterized by vertical stratification and seasonal variability in particle concentrations (Fisher et al. 1998). Particle concentrations are influenced by particles coming from the Susquehanna River, particularly in spring when there is more runoff into the river (Schubel and Biggs 1969). Total particle concentrations in the upper Bay are generally higher than in the mesohaline region (Biggs 1969). While each of these studies examined particle distributions at specific regions and sites in the Chesapeake Bay, no previous study has, to our knowledge, characterized particle size distribution across the length of the Bay. While comparing the different papers can give us insight about differences between these regions, they each use different measurements and are taken at different times. Furthermore, no study to our knowledge has examined particle size distributions within, around and above the oxygen deficient zone. Understanding particle size distribution is important because particles of different sizes can have different origins, be composed of different types of organic carbon, and be host to different chemical processes, all influencing particle dynamics. Large particles have different biology than small ones, with unique microbial communities (Mestre et al. 2017). Large particles in particular have been postulated to harbor anoxic cores which enable unique biogeochemical processes, such as reduction of nitrogen and sulfur-containing compounds (Bianchi et al. 2018; Fuschman et al. 2011). Size distribution also differs based on the main composition of particles; inorganic small particles are often dominated by clay and silt while larger inorganic particles are sand (Nichols, 1972). However, since sand does not suspend in the water column, larger particles must be comprised of lighter organic carbon, and small particles likely also contain organic carbon. Particle size information may provide clues about how much organic carbon is in suspension and its quality. Since these different materials associate with different amounts and sources of organic carbon (Burone et al. 2003), studying the size distribution in the Bay could be used to identify types of particles and the organic carbon they carry. Additionally, it has been found in oceanography that particle size distribution is the main factor determining the transfer of carbon into the deep ocean (Cram et al. 2018). Large particles sink more quickly than smaller ones, and so can more efficiently transport organic matter. Similar phenomena may occur in the Chesapeake Bay, with large and small particles having different dynamics.          The aim of the study was to describe how particle abundance and size distribution spectra of particles vary over space and depth, and in particular to identify differences between oxygenated and deoxygenated environments. Towards this end we carried out measurements of the particle size to abundance distribution and size to mass distribution along the surface and bottom of the mainstem of the Bay, from the high salinity mouth of the Bay to the lower salinity waters just below the ETM. Such data will provide information about the processes that shape particle size and transport. In particular, we are interested in how the anoxic zone affects particle dynamics, because particles attenuate slowly in anoxic regions (Rasse and Dall’Olmo 2019). Exploring the interactions between anoxic environments and particle size distributions has the potential to provide clues about how hypoxia relates to the regional carbon cycle. This study uses a combination of optical and mass measurements to characterize particle distribution throughout depth and latitude. This data is then compared with the known location of the oxygen deficient zone in the Chesapeake Bay to draw conclusions about the relationship of anoxia and particle distribution.       

Methods

Samples and observations were collected July 22, 23, and 24, 2019, on the R/V Rachel Carson from six stations along the main stem of the Chesapeake Bay, corresponding to the Maryland Department of the Environment’s water quality monitoring stations CB3.1 (39.24°N,76.24°W, corresponding to 13.3m water column depth), CB3.2 (39.16°N, 76.30 °W, 12.2 m), CB3.3C (39.00°N, 76.36°W, 24.1 m), CB4.3C (38.56°N, 76.43°W, 27.1 m), CB5.1 (38.32°N, 76.29°W, 34.3 m), and CB5.5 (37.69°N, 76.19°W, 17.7 m) (Fig. 1A).
Fig. 1 Sample Collection locations (A) and corresponding oceanographic data (B-F) measured by a seabird CTD. These included Temperature (B), Salinity (C), Fluorescence (D), pH (E), and oxygen (F). Shapes in the CTD profiles indicate the locations where particle samples were collected. Lines indicate the corresponding CTD profiles. All stations have two samples, one in the upper mixed layer, and one below, except station 4.3 which also has a sample taken at the oxycline. CTD profiles all extend from the surface to approximately 5 m above the seafloor, except station 5.5, which only extended to 15 m