Edward Callender

Nutrient exchange across the sediment-water interface in the Potomac River estuary

Abstract The flux of ammonia, phosphate, silica and radon-222 from Potomac tidal river and estuary sediments is controlled by processes occurring at the sediment-water interface and within surficial sediment. Calculated diffusive fluxes range between 0·6 and 6·5 mmol m−2 day−1 for ammonia, 0·020 and 0·30 mmol m−2 day−1 for phosphate, and 1·3 and 3·8 mmol m−2 day−1 for silica. Measured in situ fluxes range between 1 and 21 mmol m−2 day−1 for ammonia, 0·1 and 2·0 mmol m−2 day−1 for phosphate, and 2 and 19 mmol m−2 day−1 for silica. The ratio of in situ fluxes to diffusive fluxes (flux enhancement) varied between 1·6 and 5·2 in the tidal river, between 2·0 and 20 in the transition zone, and from 1·3 to 5·1 in the lower estuary. The large flux enhancements from transition zone sediments are attributed to macrofaunal irrigation. Nutrient flux enhancements are correlated with radon flux enhancements, suggesting that fluxes may originate from a common region and that nutrients are regenerated within the upper 10–20 cm of the sediment column. The low fluxes of phosphate from tidal viver sediments reflect the control benthic sediment exerts on phosphorus through sorption by sedimentary iron oxyhydroxides. In the tidal river, benthic fluxes of ammonia and phosphate equal one-half and one-third of the nutrient input of the Blue Plains sewage treatment plant. In the tidal Potomac River, benthic sediment regeneration supplies a significant fraction of the nutrients utilized by primary producers in the water column during the summer months.

Effects of colloids on metal transport in a river receiving acid mine drainage, upper Arkansas River, Colorado, U.S.A.

Abstract Inflows of metal-rich, acidic water that drain from mine dumps and tailings piles in the Leadville, Colorado, area enter the non-acidic water in the upper Arkansas River. Hydrous iron oxides precipitate as colloids and move downstream in suspension, particularly downstream from California Gulch, which has been the major source of metal loads. The colloids influence the concentrations of metals dissolved in the water and the concentrations in bed sediments. To determine the role of colloids, samples of water, colloids, and fine-grained bed sediment were obtained at stream-gaging sites on the upper Arkansas River and at the mouths of major tributaries over a 250-km reach. Dissolved and colloidal metal concentrations in the water column were operationally defined using tangential-flow filtration through 0.001-pm membranes to separate the water and the colloids. Surface-extractable and total bed sediment metal concentrations were obtained on the

Trends in metals in urban and reference lake sediments across the United States, 1970 to 2001

Trends in metals concentrations in sediment cores from 35 reservoirs and lakes in urban and reference settings were analyzed to determine the effects of three decades of legislation, regulation, and changing demographics and industrial practices in the United States on concentrations of metals in the environment. Decreasing trends outnumber increasing trends for all seven metals analyzed (Cd, Cr, Cu, Pb, Hg, Ni, and Zn). The most consistent trends are for Pb and Cr: For Pb, 83% of the lakes have decreasing trends and 6% have increasing trends; for Cr, 54% of the lakes have decreasing trends and none have increasing trends. Mass accumulation rates of metals in cores, adjusted for background concentrations, decrease from the 1970s to the 1990s, with median changes ranging from -46% (Pb) to -3% (Hg and Zn). The largest decreases are from lakes in dense urban watersheds where the overall metals contamination in recently deposited sediments has decreased to one-half its 1970s median value. However, anthropogenic mass accumulation rates in dense urban lakes remain elevated over those in lakes in undeveloped watersheds, in some cases by as much as two orders of magnitude (Cr, Cu, and Zn), indicating that urban fluvial source signals can overwhelm those from regional atmospheric sources.

Water-quality trends in White Rock Creek Basin from 1912-1994 identified using sediment cores from White Rock Lake reservoir, Dallas, Texas

Historical trends in selected water-quality variables from 1912 to 1994 in White Rock Creek Basin were identified by dated sediment cores from White Rock Lake. White Rock Lake is a 4.4-km2 reservoir filled in 1912 and located on the north side of Dallas, Texas, with a drainage area of 259 km2. Agriculture dominated land use in White Rock Creek Basin before about 1950. By 1990, 72% of the basin was urban. Sediment cores were dated using cesium-137 and core lithology. Major element concentrations changed, and sedimentation rates and percentage of clay-sized particles in sediments decreased beginning in about 1952 in response to the change in land use. Lead concentrations, normalized with respect to aluminum, were six times larger in sediment deposited in about 1978 than in pre-1952 sediment. Following the introduction of unleaded gasoline in the 1970s, normalized lead concentrations in sediment declined and stabilized at about two and one-half times the pre-1952 level. Normalized zinc and arsenic concentrations increased 66 and 76%, respectively, from before 1952 to 1994. No organochlorine compounds were detected in sediments deposited prior to about 1940. Concentrations of polychlorinated biphenyls (PCB) and DDE (a metabolite of DDT) increased rapidly beginning in the 1940s and peaked in the 1960s at 21 and 20 µg kg-1, respectively, which is coincident with their peak use in the United States. Concentrations of both declined about an order of magnitude from the 1960s to the 1990s to 3.0 and 2.0 µg kg-1, respectively. Chlordane and dieldrin concentrations increased during the 1970s and 1980s. The largest chlordane concentration was 8.0 µg kg-1 and occurred in a sediment sample deposited in about 1990. The largest dieldrin concentration was 0.7 µg kg-1 and occurred in the most recent sample deposited in the early 1990s. Agricultural use of chlordane and dieldrin was restricted in the 1970s; however, both were used as termiticides, and urban use of chlordane continued at least until 1990. Recent use of dieldrin and aldrin, which degrades to dieldrin, has not been reported; however, increasing trends in dieldrin since the 1970s suggest recent urban use could have occurred.

Greigite (Fe3S4) as an indicator of drought – The 1912–1994 sediment magnetic record from White Rock Lake, Dallas, Texas, USA

Combined magnetic and geochemical studies were conducted on sediments from White Rock Lake, a reservoir in suburban Dallas (USA), to investigate how land use has affected sediment and water quality since the reservoir was filled in 1912. The chronology of a 167-cm-long core is constrained by the recognition of the pre-reservoir surface and by 137Cs results. In the reservoir sediments, magnetic susceptibility (MS) and isothermal remanent magnetization (IRM) are largely carried by detrital titanomagnetite that originally formed in igneous rocks. Titanomagnetite and associated hematite are the dominant iron oxides in a sample from the surficial deposit in the watershed but are absent in the underlying Austin Chalk. Therefore, these minerals were transported by wind into the watershed.After about 1960, systematic decreases in Ti, Fe, and Al suggest diminished input of detrital Fe-Ti oxides from the surficial deposits. MS and IRM remain constant over this interval, however, implying compensation by an increase in strongly magnetic material derived from human activity. Anthropogenic magnetite in rust and ferrite spherules (from fly ash?) are more common in sediment deposited after about 1970 than before and may account for the constant magnetization despite the implied decrease in detrital Fe-Ti oxides.An unexpected finding is the presence of authigenic greigite (Fe3S4), the abundance of which is at least partly controlled by climate. Greigite is common in sediments that predate about 1975, with zones of concentration indicated by relatively high IRM/MS. High greigite contents in sediment deposited during the early to mid-1950s and during the mid-1930s correspond to several-year periods of below-average precipitation and drought from historical records. Relatively long water-residence times in the reservoir during these periods may have led to elevated levels of sulfate available for bacterial sulfate reduction. The sulfate was probably derived via the oxidation of pyrite that is common in the underlying Austin Chalk. These results provide a basis for the paleoenvironmental interpretation of greigite occurrence in older lake sediments. The results also indicate that greigite formed rapidly and imply that it can be preserved in the amounts produced over a short time span (in this lake, only a few years). This finding thus suggests that, in some lacustrine settings, greigite is capable of recording paleomagnetic secular variation.

Formation of ferric iron crusts in Quaternary sediments of Lake Baikal, Russia, and implications for paleoclimate

Phosphate-bearing, ferric iron and siliceous crusts ranging in age from Recent to approximately 65,000 yr B.P. are observed in sediments of Lake Baikal. In younger sediments the crusts are at the base of a spectrum of secondary iron and manganese oxides that accumulate near the sediment/water interface in the zone of positive oxidation potential beneath an oxygenated water column. In areas where the average Quaternary sedimentation rates have been slow (e.g. 0.026 mm/yr), the crusts are more common, and span a wider range of ages. No crusts have been found where the Quaternary sedimentation mode has been deltaic and rapid (0.15 mm/yr). Independent core correlation based on magnetic properties of the sediment suggests that crusts can be correlated over most of Academician Ridge, an area that is particularly sensitive to climatic events affecting the concentration of suspended sediment. These crusts may be indicative of periods of low suspended sediment concentration, which occur during sustained transitions from glacial periods of high detrital input, to interglacial periods of high diatom sedimentation. The crusts are dominated by iron-rich and siliceous amorphous mineral phases, with an FeO:SiO2by weight of 3:1. Regardless of age or location in the lake the Fe phase always includes Ca, P and Mn. Extensive microprobe data for these four elements recast as normalized elemental weight percent reveal linear trends of Ca:P and Fe:P. With increasing P, Ca also increases such that the two elements maintain a linear relationship passing very close to the origin and with a mean molar Ca:P = 0.3 (too low for well-characterized apatite). Conversely, with increasing P, Fe decreases (mean molar Fe:P = 3.4). There is no correlation between Mn and P. Molar Fe:P ratios for vivianite (an Fe(II) phosphate mineral observed in sediments closely below some crusts) are clustered around a stoichiometric composition. The covariant increase in Ca:P and the corresponding decrease in Fe:P may be explained by: (1) coupled adsorption of aqueous Ca and P by a colloidal ferric hydrous oxide; (2) loss of Fe from a Ca-P-Fe phase; or (3) oxidation of vivianite to a metastable mineral phase that gradually loses Ca and gains Fe. The first explanation is favored, because there is no petrographic evidence for either the existence of an originating Ca-P-Fe phase, or, for the oxidation of vivianite. Further, it is suggested that by continually equalizing surface charge, Ca allows more phosphate to be adsorbed leading to thicker crusts and longer preservation after burial.

Geochemical effects of rapid sedimentation in aquatic systems: Minimal diagenesis and the preservation of historical metal signatures

Rapid sedimentation exerts a pronounced influence on early sedimentary diagenesis in that there is insufficient time for a sediment particle to equilibrate in any one sediment layer before that layer may be displaced vertically by another layer. These sedimentation patterns are common in surface-water reservoirs whose sedimentation rates (1-10 cm yr-1) are several orders of magnitude greater than those for natural lakes (0.01-0.5 cm yr-1).Two examples of the effects of rapid sedimentation on geochemical metal signatures are presented here. Interstitial-water data (Fe) from two sites in the Cheyenne River Embayment of Lake Oahe on the Missouri River illustrate the effects of changing sedimentation rates on dissolved species. Rapid burial during high-flow yrs appears to limit early sedimentary diagenesis to aerobic respiration. Solid-phase metal data (Pb) from a site in Pueblo Reservoir on the upper Arkansas River in Colorado appear to record historical releases by flooding of abandoned mine sites upstream in Leadville, Colorado. Interstitial-water ammonia and ferrous Fe data indicate that at least one interval at depth in the sediment where solid metal concentrations peak is a zone of minimal diagenesis.The principal diagenetic reactions that occur in these sediments are aerobic respiration and the reduction of Mn and Fe oxides. Under slower sedimentation conditions, there is sufficient time for particulate organic matter to decompose and create a diagenetic environment where metal oxides may not be stable. The quasi-steady-state interstitial Fe profiles from Tidal Potomac River sediments are an example of such a situation. This occurs primarily because the residence time of particles in the surficial sediment column is long enough to allow benthic organisms and bacteria to perform their metabolic functions. When faster sedimentation prevails, there is less time for these metabolic reactions to occur since the organisms do not occupy a sediment layer for any length of time. Also, the quantity and quality of the organic matter input to the sediment layer is important in that reservoirs often receive more terrestrial organic matter than natural lakes and this terrestrial organic matter is generally more refractory than autochthonous aquatic organic matter.

Benthic phosphorus regeneration in the Potomac River Estuary

The flux of dissolved reactive phosphate from Potomac riverine and estuarine sediments is controlled by processes occurring at the water-sediment interface and within surficial sediment. In situ benthic fluxes (0.1 to 2.0 mmoles m−2 day−1) are generally five to ten times higher than calculated diffusive fluxes (0.020 to 0.30 mmoles m−2 day−1). The discrepancy between the two flux estimates is greatest in the transition zone (river mile 50 to 70) and is attributd to macrofaunal irrigation.

The effect of mining on the sediment - trace element geochemistry of cores from the Cheyenne River arm of Lake Oahe, South Dakota, U.S.A.

Abstract Six cores, ranging in length from 1 to 2 m, were collected in the Cheyenne River arm of Lake Oahe, South Dakota, to investigate potential impacts from gold-mining operations around Lead, South Dakota. Sedimentation rates in the river arm appear to be event-dominated and rapid, on the order of 6–7 cm yr.−1. All the chemical concentrations in the core samples fall within the wide ranges previously reported for the Pierre Shale of Cretaceous age and with the exception of As, generally are similar to bed sediment levels in the Cheyenne River, Lake Oahe and Foster Bay. Based on the downcore distribution of Mn, it appears that reducing conditions exist in the sediment column of the river arm below 2–3 cm. The reducing conditions do not appear to be severe enough to produce differentiation of Fe and Mn throughout the sediment column in the river arm. Cross-correlations for high-level metal-bearing strata within the sediment column can be made for several strata and for several cores; however, cross-correlations for all the high-level metal-bearing strata are not feasible. As is the only element which appears enriched in the core samples compared to surface sediment levels. Well-crystallized arsenopyrite was found in high-As bearing strata from two cores and probably was transported in that form from reducing sediment-storage sites in the banks or floodplains of Whitewood Creek and the Belle Fourche River. It has not oxidized due to the reducing conditions in the sediment column of the Cheyenne River arm. Some As may also be transported in association with Fe- and Mn-oxides and -hydroxides, remobilized under the reducing conditions in the river arm, and then reprecipitated in authigenic sulfide phases. In either case, the As appears to be relatively immobile in the sediment column.

Geochemistry of geopressured geothermal waters from the Frio Clay in the Gulf Coast region of Texas

Detailed chemical analyses of 54 formation-water samples from the Frio Clay from 11 oil and gas fields in the Houston-Galveston and Corpus Christi areas, Texas, indicate that the salinity of water in the geopressured zone ranges from about 20,000 to 70,000 mg/1 dissolved solids. Samples from many gas wells yield low salinities that are not representative of the true salinity of formation water because of dilution by condensed water vapor produced with natural gas. Quartz and Na-K-Ca geothermometers are used in conjunction with the measured subsurface temperatures to identify the diluted samples and to estimate their true salinities. Better understanding of the geochemistry of geopressured geothermal waters is needed to minimize the problems associated with their use as a source of energy.