Stratigraphy of total metals in PIRLA sediment cores

Sediment cores from 30 low-alkalinity lakes in northern New England (NE), New York (NY), the northern Great Lakes States (NGLS) of Minnesota, Michigan, and Wisconsin, and Florida (FL) have been dated by ²¹⁰Pb and analyzed for water and organic content, eight major elements (Al, Ti, Fe, Mn, Ca, Mg, Na, K) plus four trace metals (Pb, Zn, Cu, and V). Variations in the percentages of major elements through time are dominated by long-term independent variations in the abundance of SiO₂, FeO, and to a lesser extent Ca and Al. Additional variations are caused by varying proportions of inorganic matter. Major variations in chemistry are generally unrelated to documented distrubances in the watersheds; most disturbances are minor fires or selective logging.Accelerated accumulation of Pb from atmospheric sources into sediment first occurs in sediment dated between 1800 and 1850 in NY and NE, slightly later in the NGLS region, and about 1900 in FL. Modern accumulation rates in all areas are comparable (ca. 1 to 4 g cm^–2 yr^–1). Accumulation rates of Pb in some lakes have declined significantly from 1975 to 1985. Atmospheric deposition of anthropogenic Zn and Cu is also indicated by generally increasing accumulation rates in sediment cores, but the record is not as clear nor are chemical profiles in all lakes parallel to the trends in atmospheric emissions inferred on the basis of fossil fuel consumption, smelting, and other industrial activities. Inter-lake variations in profiles of Cu and Zn are large. Vanadium accumulation rates increase by the 1940s in NY and NE, but not until the 1950s in the NGLS region. This timing correlates with regional trends in the combustion of fuel oil, a major source of atmospheric V.Acidification of some of the lakes is suggested by decreases in the concentration and accumulation rates of Mn, Ca, and Zn in recent sediment, relative to other elements of catchment origin. The decreases generally occur slightly before the onset of acidification as indicated by diatoms. Increased sediment accumulation rates for Fe may indicate the acidification of watershed soils. The use of the accumulation rate of TiO₂ as an indicator of rates of erosion and for normalization of trace metal accumulation rates is in question for lakes where the flux of TiO₂ from the atmosphere varies and is a significant fraction of the total flux of TiO₂ to the sediment.This is the thirteenth of a series of papers to be published by this journal which is a contribution of the Paleoecological Investigation of Recent Lake Acidification (PIRLA) project. Drs. D. F. Charles and D. R. Whitehead are guest editors for this series.     

Composition and pre-metamorphic geodynamic setting of the ultrahigh-pressure metabasic rocks from Dabie Shan,E-China

As part of the Yangtze plate, segments of the Dabie Shan terrane of Central China underwent ultra-high pressure metamorphism during Triassic subduction. We studied the geochemistry of the abundant eclogites to evaluate the nature of the protoliths and their geodynamic setting. Although some previous geochemical work exists, the analyses and interpretation herein are based on a new subdivision of the ultra-high pressure sequence into basement and cover units (Changpu and Ganghe Unit), revealing new and important results. In addition, eclogites of the so-called HP Unit south of the UHP units were studied. Whereas the large ion lithophile elements indicate postmagmatic, metasomatic changes of some samples, the high-field strength elements and the rare earth elements display original magmatic trends. The geochemical characteristics of the eclogites of the ultra-high pressure areas display a strong dependence on their “structural” and geographic position. The eclogites of the basement and the Changpu Unit indicate melt intrusion and extrusion in a continental rift system, i.e. during extensional tectonics. In contrast, the Ganghe Unit is characterized by a pronounced chemical homogeneity. The composition of the eclogites indicates generation from a mantle source highly influenced by slab-derived fluids. Those of the HP Unit show similar characteristics. Magmatism of the Ganghe and HP Unit probably occurred in a continental arc setting. A similar age for both units, geographically and/or tectonically separated, is possible. The geodynamic interpretation based on the geochemistry of the four units points to a Neoproterozoic scenario in which the protoliths of the HP and the cover units could have been of similar age and deposited in one evolving geological system. A rift-related larger-scale basin might have formed, e.g. a continental back-arc basin behind a magmatic arc after or simultaneous to sedimentation and magmatism in the magmatic arc. Alternatively, magmatism occurred in independent geodynamic settings, distinct in time and space. The units were juxtaposed during exhumation, after subduction to varying depths.     

Distribution and Trophic Importance of Anthropogenic Nitrogen in Narragansett Bay: An Assessment Using Stable Isotopes

Narragansett Bay has been heavily influenced by human activities for more than 200 years. In recent decades, it has been one of the more intensively fertilized estuaries in the USA, with most of the anthropogenic nutrient load originating from sewage treatment plants (STP). This will soon change as tertiary treatment upgrades reduce nitrogen (N) loads by about one third or more during the summer. Before these reductions take place, we sought to characterize the sewage N signature in primary (macroalgae) and secondary (the hard clam, Mercenaria mercenaria) producers in the bay using stable isotopes of N (δ¹⁵N) and carbon (δ¹³C). The δ¹⁵N signatures of the macroalgae show a clear gradient of approximately 4‰ from north to south, i.e., high to low point source loading. There is also evidence of a west to east gradient of heavy to light values of δ¹⁵N in the bay consistent with circulation patterns and residual flows. The Providence River Estuary, just north of Narragansett Bay proper, receives 85% of STP inputs to Narragansett Bay, and lower δ¹⁵N values in macroalgae there reflected preferential uptake of ¹⁴N in this heavily fertilized area. Differences in pH from N stimulated photosynthesis and related shifts in predominance of dissolved C species may control the observed δ¹³C signatures. Unlike the macroalgae, the clams were remarkably uniform in both δ¹⁵N (13.2 ± 0.54‰ SD) and δ¹³C (−16.76 ± 0.61‰ SD) throughout the bay, and the δ¹⁵N values were 2–5‰ heavier than in clams collected outside the bay. We suggest that this remarkable uniformity reflects a food source of anthropogenically heavy phytoplankton formed in the upper bay and supported by sewage derived N. We estimate that approximately half of the N in the clams throughout Narragansett Bay may be from anthropogenic sources.     

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for ²⁰⁶pb/²³⁸U and 0.7392 ± 0.0003 for ²⁰⁷pb/²³⁵U. Its ²⁰⁶pb/²³⁸U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ～ 840 μg g^?1 U (Th/U ～ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 10¹⁸ g^?1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.     

Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

Long-Term Changes in Water Quality and Productivity in the Patuxent River Estuary: 1985 to 2003

We conducted a quantitative assessment of estuarine ecosystem responses to reduced phosphorus and nitrogen loading from sewage treatment facilities and to variability in freshwater flow and nonpoint nutrient inputs to the Patuxent River estuary. We analyzed a 19-year dataset of water quality conditions, nutrient loading, and climatic forcing for three estuarine regions and also computed monthly rates of net production of dissolved O₂ and physical transport of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) using a salt- and water-balance model. Point-source loading of DIN and DIP to the estuary declined by 40–60% following upgrades to sewage treatment plants and correlated with parallel decreases in DIN and DIP concentrations throughout the Patuxent. Reduced point-source nutrient loading and concentration resulted in declines in phytoplankton chlorophyll-a (chl-a) and light-saturated carbon fixation, as well as in bottom-layer O₂ consumption for upper regions of the estuary. Despite significant reductions in seaward N transport from the middle to lower estuary, chl-a, turbidity, and surface-layer net O₂ production increased in the lower estuary, especially during summer. This degradation of water quality in the lower estuary appears to be linked to a trend of increasing net inputs of DIN into the estuary from Chesapeake Bay and to above-average river flow during the mid-1990s. In addition, increased abundance of Mnemiopsis leidyi significantly reduced copepod abundance during summer from 1990 to 2002, which favored increases in chl-a and allowed a shift in total N partitioning from DIN to particulate organic nitrogen. These analyses illustrate (1) the value of long-term monitoring data, (2) the need for regional scale nutrient management that includes integrated estuarine systems, and (3) the potential water quality impacts of altered coastal food webs.     

An essay on the interactions between climate and society

There has been increasing concern about the lack of involvement by social scientists and humanists in a global change program, although many social scientists are already directly involved in various aspects of research on environmental change, and their research interests are clearly central to a global change research agenda. Based on a historical review, the role of social science disciplines as well as social science institutes in an emerging multidecadal global change program is discussed. Both “plan of action” and “plan of inaction” are suggested to avoid potential pitfalls due to the rush development of a social science program into the existing global climate change problem.     

Photochemistry and Vertical Transport in Io's Atmosphere and Ionosphere

We present an updated model for the photochemistry of Io's atmosphere and ionosphere and use this model to investigate the sensitivity of the chemical structure to vertical transport rates. SO₂is assumed to be the dominant atmospheric gas, with minor molecular sodium species such as Na₂S or Na₂O released by sputtering or venting from the surface. Photochemical products include SO, O₂, S, O, Na, NaO, NaS, and Na₂. We consider both “thick” and “thin” SO₂atmospheres that encompass the range allowed by recent HST and millimeter-wave observations, and evaluate the possibility that O₂and/or SO may be significant minor dayside constituents and therefore likely dominant nightside gases. The fast reaction between S and O₂limits the column abundance of O₂to ∼10⁴less than that calculated by Kumar (J. Geophys. Res.87, 1677–1684, 1982; 89(A9), 7399–7406, 1984) for a pure sulfur/oxygen atmosphere. If a significant source of NaO₂or Na₂O were supplied by the surface and mixed rapidly upward, then oxygen liberated in the chemical reactions which also liberate free Na would provide an additional source of O₂. Fast eddy mixing will enhance the transport of molecular sodium species to the exobase, in addition to increasing the vertical transport rate of ions. Ions produced in the atmosphere will be accelerated by the reduced corotation electric field penetrating the atmosphere. These ions experience collisions with the neutral gas, leading to enhanced vertical ion diffusion. The dominant ion, Na⁺, is lost primarily by charge exchange with Na₂O and/or Na₂S in the lower atmosphere and by diffusion through the ionopause in the upper atmosphere. The atmospheric column abundance of SO, O₂, and the upper atmosphere escape rates of Na, S, O, and molecular sodium species are all strong functions of the eddy mixing rate. Most atmospheric escape, including that of molecular sodium species, probably occurs from the low density “background” SO₂atmosphere, while a localized high density “volcanic” SO₂atmosphere can yield an ionosphere consistent with that detected by the Pioneer 10 spacecraft.