Daniel J. Bain

Down by the riverside: urban riparian ecology

Riparian areas are hotspots of interactions between plants, soil, water, microbes, and people. While urban land use change has been shown to have dramatic effects on watershed hydrology, there has been surprisingly little analysis of its effects on riparian areas. Here we examine the ecology of urban riparian zones, focusing on work done in the Baltimore Ecosystem Study, a component of the US National Science Foundation’s Long Term Ecological Research network. Research in the Baltimore study has addressed how changes in hydrology associated with urbanization create riparian “hydrologic drought” by lowering water tables, which in turn alters soil, vegetation, and microbial processes. We analyze the nature of past and current human interactions with riparian ecosystems, and review other urban ecosystem studies to show how our observations mirror those in other cities.

Quantification of Nitrate Sources to an Urban Stream Using Dual Nitrate Isotopes

Human-engineered landscapes and subsequent altered hydrology affect the fate and transport of reactive nitrogen, particularly in urban watersheds. In this study, we used dual-nitrate isotopes and mixing model analysis (δ(15)N and δ(18)O of NO3(-)) to quantify nitrogen inputs from two sources concentrated in urban systems, sewage and atmospheric deposition. Analysis was conducted on samples collected from Nine Mile Run (Pittsburgh, PA) including over two years of samples collected biweekly and samples collected through the hydrographs of four storm events. Mixing models incorporated uncertainties in the isotopic composition of potential nitrate sources and resolved the relative proportions of nitrate inputs from each source using Bayesian techniques. The results indicate that up to 94% of nitrate in streamwater originated from sewage sources during baseflow conditions. During storms, atmospheric deposition was a substantial nitrate source (∼ 34%) to total event-based nitrate loads, although sewage-derived nitrate remained the dominant source (66%). The potential influence of denitrification was considered by incorporating associated isotopic fractionations into mixing models; up to 19% of sewage-derived samples showed the isotopic effects of denitrification. This study quantitatively delineates proportions of nitrate from different sources to urban streamwater, while incorporating remaining uncertainties in source endmember compositions.

Decreased reticuloendothelial system clearance and increased blood half-life and immune cell labeling for nano- and micron-sized superparamagnetic iron-oxide particles upon pre-treatment with Intralipid.

BACKGROUND Superparamagnetic iron-oxide nanoparticles are useful as contrast agents for anatomical, functional and cellular MRI, drug delivery agents, and diagnostic biosensors. Nanoparticles are generally cleared by the reticuloendothelial system (RES), in particular taken up by Kupffer cells in the liver, limiting particle bioavailability and in-vivo applications. Strategies that decrease the RES clearance and prolong the circulation residence time of particles can improve the in-vivo targeting efficiency. METHODS Intralipid 20.0%, an FDA approved nutritional supplement, was intravenously administered in rats at the clinical dose (2g/kg) 1h before intravenous injection of ultra-small superparamagnetic iron-oxide (USPIO) or micron-sized paramagnetic iron-oxide (MPIO) particles. Blood half-life, monocyte labeling efficiency, and particle biodistribution were assessed by magnetic resonance relaxometry, flow cytometry, inductively-coupled plasma MS, and histology. RESULTS Pre-treatment with Intralipid resulted in a 3.1-fold increase in USPIO blood half-life and a 2-fold increase in USPIO-labeled monocytes. A 2.5-fold increase in MPIO blood half-life and a 5-fold increase in MPIO-labeled monocytes were observed following Intralipid pre-treatment, with a 3.2-fold increase in mean iron content up to 2.60pg Fe/monocyte. With Intralipid, there was a 49.2% and 45.1% reduction in liver uptake vs. untreated controls at 48h for USPIO and MPIO, respectively. CONCLUSIONS Intralipid pre-treatment significantly decreases initial RES uptake and increases in-vivo circulation and blood monocyte labeling efficiency for nano- and micron-sized superparamagnetic iron-oxide particles. GENERAL SIGNIFICANCE Our findings can have broad applications for imaging and drug delivery applications, increasing the bioavailability of nano- and micron-sized particles for target sites other than the liver.

Lake Sediments Record Prehistoric Lead Pollution Related to Early Copper Production in North America

The mining and use of copper by prehistoric people on Michigans Keweenaw Peninsula is one of the oldest examples of metalworking. We analyzed the concentration of lead, titanium, magnesium, iron, and organic matter in sediment cores recovered from three lakes located near mine pits to investigate the timing, location, and magnitude of ancient copper mining pollution. Lead concentrations were normalized to lithogenic metals and organic matter to account for processes that can influence natural (or background) lead delivery. Nearly simultaneous lead enrichments occurred at Lake Manganese and Copper Falls Lake ∼8000 and 7000 years before present (yr BP), indicating that copper extraction occurred concurrently in at least two locations on the peninsula. The poor temporal coherence among the lead enrichments from ∼6300 to 5000 yr BP at each lake suggests that the focus of copper mining and annealing shifted through time. In sediment younger than ∼5000 yr BP, lead concentrations remain at background levels at all three lakes, excluding historic lead increases starting ∼150 yr BP. Our work demonstrates that lead emissions associated with both the historic and Old Copper Complex tradition are detectable and can be used to determine the temporal and geographic pattern of metal pollution.

Urban legacies and soil management affect the concentration and speciation of trace metals in Los Angeles community garden soils

Heavy metals in urban soils can compromise human health, especially in urban gardens, where gardeners may ingest contaminated dust or crops. To identify patterns of urban garden metal contamination, we measured concentrations and bioavailability of Pb, As, and Cd in soils associated with twelve community gardens in Los Angeles County, CA. This included sequential extractions to partition metals among exchangeable, reducible, organic, or residual fractions. Proximity to road increased all metal concentrations, suggesting vehicle emissions sources. Reducible Pb increased with neighborhood age, suggesting leaded paint as a likely pollutant source. Exchangeable Cd and As both increased with road proximity. Only cultivated soils showed an increase in exchangeable As with road proximity, potentially due to reducing humic acid interactions while Cd bioavailability was mitigated by organic matter. Understanding the geochemical phases and metal bioavailability allows incorporation of contamination patterns into urban planning.

Constraining Nitrogen Inputs to Urban Streams from Leaking Sewers Using Inverse Modeling: Implications for Dissolved Inorganic Nitrogen (DIN) Retention in Urban Environments

Leaking sewer infrastructure contributes nonpoint nitrogen pollution to groundwater and surface water in urban watersheds. However, these inputs are poorly quantified in watershed budgets, potentially underestimating pollutant loadings. In this study, we used inverse methods to constrain dissolved inorganic nitrogen (DIN) inputs from sewage to Nine Mile Run (NMR), an urban watershed (1570 ha) in Pittsburgh, Pennsylvania (USA) characterized by extensive impervious surface cover (38%). Water samples were collected biweekly over two years and intensive sampling was conducted during one summer storm. A nitrogen budget for the NMR watershed was constructed, ultimately inverted, and sewage DIN inputs constrained using Monte Carlo simulation. Results reveal substantial DIN contributions from sewage ranging from 6 to 14 kg ha-1 yr-1. When conservative estimates of DIN from sewage are included in input calculations, DIN retention in NMR is comparable to high rates observed in other suburban/urban nutrient budgets (84%). These results suggest a pervasive influence of leaking sewers during baseflow conditions and indicate that sewage-sourced DIN is not limited to sewer overflow events. Further, they highlight the importance of sewage inputs to DIN budgets in urban streams, particularly as sewer systems age across the U.S.

Assessment of Regional Variation in Streamflow Responses to Urbanization and the Persistence of Physiography

Aquatic ecosystems are sensitive to the modification of hydrologic regimes, experiencing declines in stream health as the streamflow regime is altered during urbanization. This study uses streamflow records to quantify the type and magnitude of hydrologic changes across urbanization gradients in nine U.S. cities (Atlanta, GA, Baltimore, MD, Boston, MA, Detroit, MI, Raleigh, NC, St. Paul, MN, Pittsburgh, PA, Phoenix, AZ, and Portland, OR) in two physiographic settings. Results indicate similar development trajectories among urbanization gradients, but heterogeneity in the type and magnitude of hydrologic responses to this apparently uniform urban pattern. Similar urban patterns did not confer similar hydrologic function. Study watersheds in landscapes with level slopes and high soil permeability had less frequent high-flow events, longer high-flow durations, lower flashiness response, and lower flow maxima compared to similarly developed watersheds in landscape with steep slopes and low soil permeability. Our results suggest that physical characteristics associated with level topography and high water-storage capacity buffer the severity of hydrologic changes associated with urbanization. Urbanization overlain upon a diverse set of physical templates creates multiple pathways toward hydrologic impairment; therefore, we caution against the use of the urban homogenization framework in examining geophysically dominated processes.

Placing the pieces: Reconstructing the original property mosaic in a warrant and patent watershed

Recent research shows that land use history is an important determinant of current ecosystem function. In the United States, characterization of land use change following European settlement requires reconstruction of the original property mosaic. However, this task is difficult in unsystematically surveyed areas east of the Appalachian Mountains. The Gwynns Falls watershed (Baltimore, MD) was originally surveyed in the 1600-1700s under a system of warrants and patents (commonly known as ‘metes and bounds’). A method for the reconstruction and mapping of warrant and patent properties is presented and used to map the original property mosaic in the Gwynns Falls watershed. Using the mapped mosaic, the persistence of properties and property lines in the current Gwynns Falls landscape is considered. The results of this research indicate that as in agricultural areas, the original property lines in the Gwynns Falls watershed are persistent. At the same time, the results suggest that the property mosaic in heavily urbanized/suburbanized areas is generally ‘reset.’ Further, trends in surveying technique, parcel size, and settlement patterns cause property line density and property shape complexity to increase in the less urbanized upper watershed. The persistence of original patterns may be damping expression of heterogeneity gradients in this urban landscape. This spatial pattern of complexity in the original mosaic is directly opposite of hypothesized patterns of landscape heterogeneity arising from urbanization. The technique reported here and the resulting observations are important for landscape pattern studies in areas settled under unsystematic survey systems, especially the heavily urbanized areas of the eastern United States.

Environmental Legacy of Copper Metallurgy and Mongol Silver Smelting Recorded in Yunnan Lake Sediments

Geochemical measurements on well-dated sediment cores from Lake Er (Erhai) are used to determine the timing of changes in metal concentrations over 4500 years in Yunnan, a borderland region in southwestern China noted for rich mineral deposits but with inadequately documented metallurgical history. Our findings add new insight into the impacts and environmental legacy of human exploitation of metal resources in Yunnan history. We observe an increase in copper at 1500 BC resulting from atmospheric emissions associated with metallurgy. These data clarify the chronological issues related to links between the onset of Yunnan metallurgy and the advent of bronze technology in adjacent Southeast Asia, subjects that have been debated for nearly half a century. We also observe an increase from 1100 to 1300 AD in a number of heavy metals including lead, silver, zinc, and cadmium from atmospheric emissions associated with silver smelting. Culminating during the rule of the Mongols, known as the Yuan Dynasty (1271-1368 AD), these metal concentrations approach levels three to four times higher than those from industrialized mining activity occurring within the catchment today. Notably, the concentrations of lead approach levels at which harmful effects may be observed in aquatic organisms. The persistence of this lead pollution over time created an environmental legacy that likely contributes to known issues in modern day sediment quality. We demonstrate that historic metallurgical production in Yunnan can cause substantial impacts on the sediment quality of lake systems, similar to other paleolimnological findings around the globe.

Metal concentrations in urban riparian sediments along an urbanization gradient

Urbanization impacts fluvial systems via a combination of changes in sediment chemistry and basin hydrology. While chemical changes in urban soils have been well characterized, similar surveys of riparian sediments in urbanized areas are rare. Metal concentrations were measured in sediments collected from riparian areas across the urbanization gradient in Baltimore, MD. Average metal concentrations are similar to those observed in other regional studies. Two important spatial patterns are evident in the data. First, calcium concentrations double across the urbanization gradient, regardless of changes in underlying geochemistry at the boundary between the Eastern US Piedmont and Coastal Plain physiographic provinces. Alkali-earth metal ratios indicate that the additional Ca is very pure and possibly arises from cement common to urban systems. Second, hot spots of trace metals typically associated with urban systems (e.g., Cu, Zn, and Pb) occur in areas that have been artificially filled to create additional real estate in high land value areas. Together, these data indicate that riparian sediments exhibit unexpected patterns of metal contamination. If these sediments are remobilized, during events such as droughts or floods, this contamination may perpetuate legacy impacts to ecosystem health from a history of fluvial contamination.