Field and Laboratory Studies of Atmospheric Organic Aerosol

This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation.

The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate.

Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f₄₂ and f₉₉) was found to coincide with periods of heavy (f₄₂ > 0.15; f₉₉ > 0.04), moderate (0.05 < f₄₂ < 0.15; 0.01 < f₉₉ < 0.04), and negligible (f₄₂ < 0.05; f₉₉ < 0.01) ship influence. Application of these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( < 1 hr) compared to the time needed for particles to become hygroscopic at sub-saturated humidity ( > 4 hr).

Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate.

Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary oxidation mechanism is suggested to be a combination of Fenton and photo-Fenton reactions which enhance particle-phase OH radical concentrations.

Marine biology of the Sierra Leone River Estuary. 1. The physical environment

The Sierra Leone River Estuary is a relatively young drowned river valley, it is shallow except for a deep channel which passes close to the Freetown shoreline. The upper reaches merge into a network of creeks and channels fringed by large areas of mangrove swamps. It is a tidal estuary of the semi-mixed type with the saline oceanic water entering it on a diurnal cycle. The climate of Sierra Leone is marked by a very distinct change between a very wet rainy season and a dry season. The tidal range of the Estuary (spring 3.03m; neap 2.28m) does not impede normal use of the harbour. The tidal variations can be felt as far as 42 miles inland along the water courses of the Sierra Leone River and its tributaries. The volume of fresh water entering the Estuary is large during the rainy season and greatly reduced during the dry season. Consequently there is a marked fall in salinity during the rainy season and higher salinities due to the marine influence prevailing during the dry season. The nature of the shores and bottom, the hydrography and chemistry of the estuarine system have been outlined in relation to the prevailing climatic conditions.

Hypoxic and low pH water in the nearshore marine environments of Monterey Bay, California: characterizing a decade of oxygen and pH, and drivers of variability.

A decade-long time series recorded in southern Monterey Bay, California demonstrates that the shallow, near-shore environment (17 m depth) is regularly inundated with pulses of cold, hypoxic and low pH water. During these episodes, oxygen can drop to biologically threatening levels, and pH levels were lower than expected. Weekly water chemistry monitoring revealed that the saturation state of aragonite (the more soluble form of calcium carbonate) was often below saturation and had a moderate positive relationship with pH, however, analytical and human error could be high. Pulses of hypoxia and low pH water with the greatest intensity arise at the onset of the spring upwelling season, and fluctuations are strongly semidurnal (tidal) and diurnal. Arrival of cold, hypoxic water on the inner shelf typically occurs 3 days after the arrival of a strong upwelling event and appears to be driven by upwelling modulated by internal tidal fluctuations. I found no relationship between the timing of low-oxygen events and the diel solar cycle nor with terrestrial nutrient input. These observations are consistent with advection of hypoxic water from the deep, offshore environment where water masses experience a general decline of temperature, oxygen and pH with depth, and inconsistent with biochemical forcing. Comparisons with concurrent temperature and oxygen time series taken ~20 km away at the head of the Monterey Canyon show similar patterns but even more intense hypoxic events due to stronger semidiurnal forcing there. Analysis of the durations of exposure to low oxygen levels establishes a framework for assessing the ecological relevance of these events. Increasing oceanic hypoxia and acidification of both surface and deep waters may increase the number, intensity, duration and spatial extent of future intrusions along the Pacific coast. Evaluation of the resiliency of nearshore ecosystems such as kelp forests, rocky reefs and sandy habitats, will require consideration of these events.

Season- and depth-dependent variability of a demersal fish assemblage in a large fjord estuary (Puget Sound, Washington)

Fjord estuaries are common along the northeast Pacific coastline, but little information is available on fish assemblage structure and its spatiotemporal variability. Here, we examined changes in diversity metrics, species biomasses, and biomass spectra (the distribution of biomass across body size classes) over three seasons (fall, winter, summer) and at multiple depths (20 to 160 m) in Puget Sound, Washington, a deep and highly urbanized fjord estuary on the U.S. west coast. Our results indicate that this fish assemblage is dominated by cartilaginous species (spotted ratfish [Hydrolagus colliei] and spiny dogfish [Squalus acanthias]) and therefore differs fundamentally from fish assemblages found in shallower estuaries in the northeast Pacific. Diversity was greatest in shallow waters (<40 m), where the assemblage was composed primarily of flatfishes and sculpins, and lowest in deep waters (>80 m) that are more common in Puget Sound and that are dominated by spotted ratf ish and seasonally (fall and summer) by spiny dogfish. Strong depth-dependent variation in the demersal fish assemblage may be a general feature of deep fjord estuaries and indicates pronounced spatial variability in the food web. Future comparisons with less impacted fjords may offer insight into whether cartilaginous species naturally dominate these systems or only do so under conditions related to human-caused ecosystem degradation. Information on species distributions is critical for marine spatial planning and for modeling energy flows in coastal food webs. The data presented here will aid these endeavors and highlight areas for future research in this important yet understudied system.

Anadromous fish as marine nutrient vectors

The tidal freshwater of Virginia supports anadromous herring (Alosa spp.) spawning runs in the spring; however, their importance as nutrient delivery vectors to the freshwater fish food web remains unknown. The stable isotope signatures of fishes from 21 species and four different guilds (predators, carnivores, generalists, and planktivores) were examined in this study to test the hypothesis that marine derived nutrients (MDNs) brought by anadromous fish would be traced into the guilds that incorporated them. Spawning anadromous fish were 13C and 34S-enriched (δ13C and δ34S of approximately 18‰ and 17.7‰, respectively) relative to resident freshwater fish. Of the guilds examined, only predators showed 13C and 34S-enrichment similar to the anadromous fish; however, some generalist catfish also showed enriched signatures. Specific fatty acid δ13C signatures for gizzard shad (Dorosoma cepedianum), blue catfish (Ictalurus furcatus), and alewife (Alosa pseudoharengus), show a 10‰ range among fishes, clearly reflecting isotopically distinct dietary sources. The δ13C and δ34S distribution and range among the freshwater fishes suggest that both autochthonous and allochthonous (terrestrial C3 photosynthetic production and MDN) nutrient sources are important to the tidal freshwater fish community.

Diet composition and food habits of demersal and pelagic marine fishes from Terengganu waters, east coast of Peninsular Malaysia

Fish stomachs from 18 demersal and pelagic fishes from the coast of Terengganu in Malaysia were examined. The components of the fishes’ diets varied in number, weight, and their frequency of occurrence. The major food items in the stomachs of each species were determined using an Index of Relative Importance. A conceptual food web structure indicates that fish species in the study area can be classified into three predatory groups: (1) predators on largely planktivorous or pelagic species; (2) predators on largely benthophagous or demersal species; and (3) mixed feeders that consume both pelagic and demersal species.

Temporal Changes in a Tropical Nekton Assemblage and Performance of a Prawn Selective Gear

The temporal variation of components of a moderately diverse (H=1.46) tropical estuarine fish assemblage (long. 146°30'E, lat. 8°45'S) was directed by salinities that had been determined by local oceanographic and probably topographic conditions. For this assemblage, two types of intrayear component profiles are predicted. Pooled data (1988-91) reveal a large component of regular/resident species (43%) in an assemblage which has been under a narrow temperature regime «5T). These results facilitate a discussion on the relevance and usefulness of three hypotheses often cited in studies concerning species diversity and component characteristics of the subtropical/tropical coastal nonreef fish assemblages. Manifestations of the assemblage are reflected in catch composition and weights of 39 trials conducted for a selective prawning gear whose performance in bycatch reduction, mainly for finfishes, is judged by an index, E, we have previously proposed. This gear is capable of harvesting the prawn while conserving the demersal fish. Behavioral responses to netting of the prawns and the finfishes, especially the nearshore surface schoolers such as leiognathids, are discussed from several points of view. An adaptation in terms of group selection for leiognathids of their locking mechanism of median fin spines has been interpreted. For the purpose of bycatch reduction or E enhancement, suggestions for improvements in net design and trawl configuration by considering the behavioral features of fish are made. Our original formula of E is modified for general use. Bycatch problems in the regional prawn fisheries and their possible impacts on fishery planning and development in Papua New Guinea as a developing country are discussed. The gear tested may offer enormous ecological and economic benefits. The gear is multipurpose, extremely simple, and can also be used as a biological sampler.

Travel Characteristics of Marine Anglers Using Oil and Gas Platforms in the Central Gulf of Mexico

This study was designed to evaluate the travel characteristics of avid marine anglers off Louisiana in the Central Gulf of Mexico. It focuses on the complex marine travel patterns involving the extensive assemblage of oil and gas structures. In an intercept approach, marine recreationalf isherman were asked to identify near and offshore travel patterns on the day of the interview. Information was also solicited regarding how respondents selected and located fishing destinations as well as what method of fishing was undertaken that day. Petroleum platforms were a principal fishing destination, and platform anglers traveled an average distance of 75.5 km (40.7 n.mi.) to and from offshore fishing locations. In fishing an average of 6.5 platforms per trip, these anglers traveled about 21.3 km (11.5 n.mi.) between the first and last platform visited. Mean total distances for platform anglers were 96 km (51.8 n.mi). Travel distances for bay, nearshore, and bluewater anglers were also obtained.

Seasonal and interannual variation in juvenile salmonids and associated fish assemblage in open waters of the lower Columbia River estuary

The transition between freshwater and marine environments is associated with high mortality for juvenile anadromous salmonids, yet little is known about this critical period in many large rivers. To address this deficiency, we investigated the estuarine ecology of juvenile salmonids and their associated fish assemblage in open-water habitats of the lower Columbia River estuary during spring of 2007–10. For coho (Oncorhynchus kisutch), sockeye (O. nerka), chum (O. keta), and yearling (age 1.0) Chinook (O. tshawytscha) salmon, and steelhead (O. mykiss), we observed a consistent seasonal pattern characterized by extremely low abundances in mid-April, maximum abundances in May, and near absence by late June. Subyearling (age 0.0) Chinook salmon were most abundant in late June. Although we observed interannual variation in the presence, abundance, and size of juvenile salmonids, no single year was exceptional across all species-and-age classes. We estimated that >90% of juvenile Chinook and coho salmon and steelhead were of hatchery origin, a rate higher than previously reported. In contrast to juvenile salmonids, the abundance and composition of the greater estuarine fish assemblage, of which juvenile salmon were minor members, were extremely variable and likely responding to dynamic physical conditions in the estuary. Comparisons with studies conducted 3 decades earlier suggest striking changes in the estuarine fish assemblage—changes that have unknown but potentially important consequences for juvenile salmon in the Columbia River estuary.

The Southeast Bering Sea Ecosystem: implications for marine resource management (Final Report: Southeast Bering Sea Carrying Capacity).

Southeast Bering Sea Carrying Capacity (SEBSCC, 1996–2002) was a NOAA Coastal Ocean Program project that investigated the marine ecosystem of the southeastern Bering Sea. SEBSCC was co-managed by the University of Alaska Fairbanks, NOAA Alaska Fisheries Science Center, and NOAA Pacific Marine Environmental Laboratory. Project goals were to understand the changing physical environment and its relationship to the biota of the region, to relate that understanding to natural variations in year-class strength of walleye pollock (Theragra chalcogramma), and to improve the flow of ecosystem information to fishery managers. In addition to SEBSCC, the Inner Front study (1997–2000), supported by the National Science Foundation (Prolonged Production and Trophic Transfer to Predators: Processes at the Inner Front of the S.E. Bering Sea), was active in the southeastern Bering Sea from 1997 to 1999. The SEBSCC and Inner Front studies were complementary. SEBSCC focused on the middle and outer shelf. Inner Front worked the middle and inner shelf. Collaboration between investigators in the two programs was strong, and the joint results yielded a substantially increased understanding of the regional ecosystem. SEBSCC focused on four central scientific issues: (1) How does climate variability influence the marine ecosystem of the Bering Sea? (2) What determines the timing, amount, and fate of primary and secondary production? (3) How do oceanographic conditions on the shelf influence distributions of fish and other species? (4) What limits the growth of fish populations on the eastern Bering Sea shelf? Underlying these broad questions was a narrower focus on walleye pollock, particularly a desire to understand ecological factors that affect year-class strength and the ability to predict the potential of a year class at the earliest possible time. The Inner Front program focused on the role of the structural front between the well-mixed waters of the coastal domain and the two-layer system of the middle domain. Of special interest was the potential for prolonged post-spring-bloom production at the front and its role in supporting upper trophic level organisms such as juvenile pollock and seabirds. Of concern to both programs was the role of interannual and longer-term variability in marine climates and their effects on the function of sub-arctic marine ecosystems and their ability to support upper trophic level organisms.

Status of coral reef ecosystems in a marine managed area in St. Croix, USVI [poster]

This poster presents information on the status and trends of coral reef ecosystems in St. Croix, US Virgin Islands (USVI). Data were collected by NOAA’s Center for Coastal Monitoring and Assessment Biogeography Branch (CCMA-BB) from 2001-2006 at 1,275 random locations in and around Buck Island Reef National Monument (BIRNM). The main objective was to quantify changes in fish species and assemblage diversity, abundance, biomass and size structure; to provide spatially explicit information on the distribution of key species or groups of species; and to compare community structure inside versus outside of BIRNM.

Marine fish assemblages associated with fish aggregating devices (FADs): effects of fish removal, FAD size, fouling communities, and prior recruits

Fishes are widely known to aggregate around floating objects, including flotsam and fish aggregating devices (FADs).The numbers and diversity of juvenile fishes that associated with floating objects in the nearshore waters of the eastern tropical Pacific were recording by using FADs as an experimental tool. The effects of fish removal, FAD size, and the presence or absence of a fouling community at the FAD over a period of days, and the presence of prior recruits over a period of hours were evaluated by using a series of experiments. The removal of FAD-associated fish assemblages had a significant effect on the number of the dominant species (Abudefduf troschelii) in the following day’s assemblage compared to FADs where the previous day’s assemblage was undisturbed; there was no experimental effect on combined species totals. Fishes do, however, discriminate among floating objects, forming larger, more species-rich assemblages around large FADs compared to small ones. Fishes also formed larger assemblages around FADs possessing a fouling biota versus FADs without a fouling biota, although this effect was also closely tied to temporal factors. FADs enriched with fish accumulated additional recruits more quickly than FADs that were not enriched with fish and therefore the presence of prior recruits had a strong, positive effect on subsequent recruitment. These results suggest that fish recruitment to floating objects is deliberate rather than haphazard or accidental and they sup-port the hypothesis that flotsam plays a role in the interrelationship between environment and some juvenile fishes. These results are relevant to the use of FADs for fisheries, but emphasize that further research is necessary for applied interests.

Note on the occurrence of a terrestrial isopod, Hemilepistus klugii (Brandt) in Baluchistan, Pakistan

During a computer-aided search of the Crustacea collection in the Department of Invertebrate Zoology at the Smithsonian Institution (USNM), a record was found for the existence of Hemilepistus klugii (Brandt, 1833) in Pakistan.

Some observations on the problem of marine timber destroying organisms of Indian coasts

In India the chief marine timber boring organisms are 2 species of Martesia, 28 species of shipworms, 4 species and a variety of Sphaeroma and 9 species of Limnoria besides bacteria and fungi. The occurrence, abundance and activity of the various species of borers show remarkable variations and fluctuations in the different harbours of India, each harbour or area having its own dominant set of species and an assemblage of less important forms. These species have their own characteristic preferences, life history and seasons of attachment and a scheme evolved for one locality may prove ineffective for another. Through a delicate and complex ecological adjustment the borers occurring in a locality have reached an interrelationship reducing interspecific and intraspecific competition. The seasons of settlement of the dominant borers in the different harbours of India are indicated. The need for a detailed biological enquiry is stressed.

Seasonal variation of mixed layer depth in the north Arabian Sea

The Arabian Sea is unique due to the extremes in atmospheric forcing that lead to the semi-annual seasonal changes. The reversing winds of summer and winter monsoon induce the variation in the characteristics of mixed layer depth. The importance of mixed layer depth is recognized in studying the biological productivity in the ocean. In this paper variability of mixed layer depth in the north Arabian Sea have been discussed. The study is based on the data collected under North Arabian Sea Environment and Ecosystem Research (NASEER) program. The results of the study indicate that there is a significant variation in the mixed layer depth from summer to winter monsoon as well as coast to offshore.