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Linda H. Kalnejais

Publications and source records attributed to Linda H. Kalnejais.

5 recordsLinked to original sources

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

Massachusetts

Role of sediment resuspension in the remobilization of particulate-phase metals from coastal sediments

The release of particulate-phase trace metals due to sediment resuspension has been investigated by combining erosion chamber experiments that apply a range of shear stresses typically encountered in coastal environments with a shear stress record simulated by a hydrodynamic model. Two sites with contrasting sediment chemistry were investigated. Sediment particles enriched in silver, copper, and lead, 4−50 times greater than the bulk surface-sediment content, were the first particles to be eroded. As the shear-stress level was increased in the chamber, the total mass eroded increased, but the enrichment of these trace metals fell, approaching the bulk-sediment content. From the temporal distribution of shear stress generated by the hydrodynamic model for a site in Boston Harbor, resuspension fluxes were estimated. The erosion threshold of this site is exceeded during spring tides, releasing the particles enriched in trace metals into the water column. Due to the higher trace metal content and the regularity of resuspension, low-energy resuspension events (up to a shear stress of 0.2 N/m 2 ) contribute up to 60% of the resuspension metal flux in an average year. The estimated annual quantity of copper and lead resuspended into the water column is higher than estimates of the total riverine flux for these metals. These results indicate that sediment resuspension is a very important mechanism for releasing metals into the water column and provide new insight into the chemical and physical processes controlling the long-term fate of trace metals in contaminated sediments.

Massachusetts

Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA

This study examined the removal of U, Mo, and Re from seawater by sedimentary processes at a shallow-water site with near-saturation bottom water O 2 levels (240–380 μmol O 2 /L), very high organic matter oxidation rates (annually averaged rate is 880 μmol C/cm 2 /y), and shallow oxygen penetration depths (4 mm or less throughout the year). Under these conditions, U, Mo, and Re were removed rapidly to asymptotic pore water concentrations of 2.2–3.3 nmol/kg (U), 7–13 nmol/kg (Mo), and 11–14 pmol/kg (Re). The depth order in which the three metals were removed, determined by fitting a diffusion-reaction model to measured profiles, was Re < U < Mo. Model fits also suggest that the Mo profiles clearly showed the presence of a near-interface layer in which Mo was added to pore waters by remineralization of a solid phase. The importance of this solid phase source of pore water Mo increased from January to October as the organic matter oxidation rate increased, bottom water O 2 decreased, and the O 2 penetration depth decreased. Experiments with in situ benthic flux chambers generally showed fluxes of U and Mo into the sediments. However, when the overlying water O 2 concentration in the chambers was allowed to drop to very low levels, Mn and Fe were released to the overlying water along with the simultaneous release of Mo and U. These experiments suggest that remineralization of Mn and/or Fe oxides may be a source of Mo and perhaps U to pore waters, and may complicate the accumulation of U and Mo in bioturbated sediments with high organic matter oxidation rates and shallow O 2 penetration depths. Benthic chamber experiments including the nonreactive solute tracer, Br − , indicated that sediment irrigation was very important to solute exchange at the study site. The enhancement of sediment–seawater exchange due to irrigation was determined for the nonreactive tracer (Br − ), TCO 2 , NH 4 + "> NH 4 + , U and Mo. The comparisons between these solutes showed that reactions within and around the burrows were very important for modulating the Mo flux, but less important for U. The effect of these reactions on Mo exchange was highly variable, enhancing Mo (and, to a lesser extent, U) uptake at times of relatively modest irrigation, but inhibiting exchange when irrigation rates were faster. These results reinforce the observation that Mo can be released to and removed from pore waters via sedimentary reactions. The removal rate of U and Mo from seawater by sedimentary reactions was found to agree with the rate of accumulation of authigenic U and Mo in the solid phase. The fluxes of U and Mo determined by in situ benthic flux chamber measurements were the largest that have been measured to date. These results confirm that removal of redox-sensitive metals from continental margin sediments underlying oxic bottom water is important, and suggest that continental margin sediments play a key role in the marine budgets of these metals.

Geochimica et Cosmochimica Acta

Processes influencing the transport and fate of contaminated sediments in the coastal ocean– Boston Harbor and Massachusetts Bay

Most of the major urban centers of the United States including Boston, New York, Washington, Chicago, New Orleans, Miami, Los Angeles, San Francisco, and Seattle—are on a coast (fig. 1.1). All of these cities discharge treated sewage effluent into adjacent waters. In 2000, 74 percent of the U.S. population lived within 200 kilometers (km) of the coast. Between 1980 and 2002, the population density in coastal communities increased approximately 4.5 times faster than in noncoastal areas of the U.S. (Perkins, 2004). More people generate larger volumes of wastes, increase the demands on wastewater treatment, expand the area of impervious land surfaces, and use more vehicles that contribute contaminants to street runoff. According to the National Coastal Condition Report II (U.S. Environmental Protection Agency, 2005a), on the basis of coastal habitat, water and sediment quality, benthic index, and fish tissue, the overall national coastal condition is only poor to fair and the overall coastal condition in the highly populated Northeast is poor. Scientific information helps managers to prioritize and regulate coastal-ocean uses that include recreation, commercial fishing, transportation, waste disposal, and critical habitat for marine organisms. These uses are often in conflict with each other and with environmental concerns. Developing a strategy for managing competing uses while maintaining sustainability of coastal resources requires scientific understanding of how the coastal ocean system behaves and how it responds to anthropogenic influences. This report provides a summary of a multidisciplinary research program designed to improve our understanding of the transport and fate of contaminants in Massachusetts coastal waters. Massachusetts Bay and Boston Harbor have been a focus of U.S. Geological Survey (USGS) research because they provide a diverse geographic setting for developing a scientific understanding of the geology, geochemistry, and oceanography of coastal systems in general. Scientific data from this region can also be used to inform decisions about important economic, environmental, and political issues. From the economic viewpoint, the annual value of tourism and shipping in Massachusetts and Cape Cod Bays is about $1.5 billion and $1.9 billion, respectively. Commercial and recreational fishing generates about $240 million per year in the same region (U.S. Environmental Protection Agency, 2005b). The environmental issue is the 300-year history of waste discharge from the Boston metropolitan area into the harbor. This history is punctuated by cycles of environmental degradation, public outcry, and improvements in the sewage treatment system. With each improvement, however, the continuous growth of population in greater Boston (fig. 1.2) and the resulting increase in the volume of waste exceeded the capacity of the treatment system, thereby setting the stage for a new contamination crisis. By the 1980s, the levels of contaminants in sediments of Boston Harbor were among the highest in the nation (National Oceanic and Atmospheric Administration, 1987). Fish were diseased, shellfish beds were closed, and swimming beaches were unsafe after heavy rains; in general, water quality and aesthetics were below acceptable standards. Legal and political issues have always been part of Boston Harbor’s history. The environmental conditions in the 1980s were highlighted in a 1983 legal suit brought by the city of Quincy against the Metropolitan District Commission (MDC, the state agency responsible for sewage treatment) and heads of three state agencies for discharging untreated or poorly treated sewage into the harbor (Dolin, 2004). The suit never went to trial, but through the actions of a Massachusetts Superior Court, the issue of Boston Harbor contamination remained on the political and public agenda. The judge called the harbor “unsafe, unsanitary, indecent, in violation of the law (Clean Water Act), and a danger to the health and welfare of the people” (Forman, 1984). To force the state legislature to implement a plan to improve harbor conditions, the judge threatened to place the MDC in receivership and curtail new sewage hookups for industry. Under intense lobbying by business, the legislature created the Massachusetts Water Resources Authority (MWRA) in December 1984. The independent MWRA was established to manage Boston’s waste treatment system and was given the authority to float bonds to pay for major improvements in the treatment system. In 1985, a Federal court began hearings on a suit brought by the Conservation Law Foundation, the Environmental Protection Agency (USEPA), and towns of Quincy and Winthrop against the MDC and MWRA (as heir to responsibilities of the MDC) for years of violation of the Clean Water Act. The judge ruled against the defendants and required all the parties to submit a construction plan and schedule for a new sewage treatment system. From these submissions, he developed a schedule for treatment system upgrades that would give the “citizens of this commonwealth a public assurance that Boston Harbor will be cleaned up within a defined period of time” (Dolin, 2004). The MWRA’s Boston Harbor cleanup program (Levy and Connor, 1992) has transformed the Boston sewage system. Key improvements were to (1) reduce contaminants at the industrial source; (2) remediate leaks in the sewage-collection system; (3) eliminate sewage sludge discharge to the harbor; (4) upgrade sewage treatment from primary to secondary; (5) construct a new ocean outfall 15.2 km offshore in Massachusetts Bay for discharge of treated effluent (fig. 1.3); and (6) implement improvements in the combined-sewer-overflow system. As part of the harbor cleanup program, the MWRA developed a comprehensive monitoring program (summarized in MWRA, 2004) to assess changes in the harbor and bays that specifically related to the new sewage system. Additional information about conditions and processes in the coastal system on a regional scale and over a long time period was and continues to be important in predicting and interpreting local change. Implementation of the MWRA’s program and the mission of the USGS to understand the geology of the nation’s offshore waters provided an opportunity to conduct a cooperative multidisciplinary research program. This USGS program addresses basic scientific questions as well as concerns raised by management regarding the design, implementation, and assessment of the new sewage treatment system. Already active in Boston Harbor during the late 1970s, the USGS expanded research into Massachusetts Bay with a multidisciplinary program in 1989.

Massachusetts