Gary S. Dwyer

Medieval Warm Period, Little Ice Age and 20th century temperature variability from Chesapeake Bay

We present paleoclimate evidence for rapid (<100 years) shifts of f2–4 jC in Chesapeake Bay (CB) temperature f2100, 1600, 950, 650, 400 and 150 years before present (years BP) reconstructed from magnesium/calcium (Mg/Ca) paleothermometry. These include large temperature excursions during the Little Ice Age (f1400–1900 AD) and the Medieval Warm Period (f800–1300 AD) possibly related to changes in the strength of North Atlantic thermohaline circulation (THC). Evidence is presented for a long period of sustained regional and North Atlantic-wide warmth with low-amplitude temperature variability between f450 and 1000 AD. In addition to centennial-scale temperature shifts, the existence of numerous temperature maxima between 2200 and 250 years BP (average f70 years) suggests that multi-decadal processes typical of the North Atlantic Oscillation (NAO) are an inherent feature of late Holocene climate. However, late 19th and 20th century temperature extremes in Chesapeake Bay associated with NAO climate variability exceeded those of the prior 2000 years, including the interval 450–1000 AD, by 2–3 jC, suggesting anomalous recent behavior of the climate system. D 2002 Elsevier Science B.V. All rights reserved.

North Atlantic Deepwater Temperature Change During Late Pliocene and Late Quaternary Climatic Cycles

Variations in the ratio of magnesium to calcium (Mg/Ca) in fossil ostracodes from Deep Sea Drilling Project Site 607 in the deep North Atlantic show that the change in bottom water temperature during late Pliocene 41,000-year obliquity cycles averaged 1.5°C between 3.2 and 2.8 million years ago (Ma) and increased to 2.3°C between 2.8 and 2.3 Ma, coincidentally with the intensification of Northern Hemisphere glaciation. During the last two 100,000-year glacial-to-interglacial climatic cycles of the Quaternary, bottom water temperatures changed by 4.5°C. These results show that glacial deepwater cooling has intensified since 3.2 Ma, most likely as the result of progressively diminished deepwater production in the North Atlantic and of the greater influence of Antarctic bottom water in the North Atlantic during glacial periods. The ostracode Mg/Ca data also allow the direct determination of the temperature component of the benthic foraminiferal oxygen isotope record from Site 607, as well as derivation of a hypothetical sea-level curve for the late Pliocene and late Quaternary. The effects of dissolution on the Mg/Ca ratios of ostracode shells appear to have been minimal.

Interlaboratory comparison study of Mg/Ca and Sr/Ca measurements in planktonic foraminifera for paleoceanographic research

Thirteen laboratories from the USA and Europe participated in an intercomparison study of Mg/Ca and Sr/Ca measurements in foraminifera. The study included five planktonic species from surface sediments from different geographical regions and water depths. Each of the laboratories followed their own cleaning and analytical procedures and had no specific information about the samples. Analysis of solutions of known Mg/Ca and Sr/Ca ratios showed that the intralaboratory instrumental precision is better than 0.5% for both Mg/Ca and Sr/Ca measurements, regardless whether ICP-OES or ICP-MS is used. The interlaboratory precision on the analysis of standard solutions was about 1.5% and 0.9% for Mg/Ca and Sr/Ca measurements, respectively. These are equivalent to Mg/Ca-based temperature repeatability and reproducibility on the analysis of solutions of ±0.2°C and ±0.5°C, respectively. The analysis of foraminifera suggests an interlaboratory variance of about ±8% (%RSD) for Mg/Ca measurements, which translates to reproducibility of about ±2–3°C. The relatively large range in the reproducibility of foraminiferal analysis is primarily due to relatively poor intralaboratory repeatability (about ±1–2°C) and a bias (about 1°C) due to the application of different cleaning methods by different laboratories. Improving the consistency of cleaning methods among laboratories will, therefore, likely lead to better reproducibility. Even more importantly, the results of this study highlight the need for standards calibration among laboratories as a first step toward improving interlaboratory compatibility.

Mid-Cretaceous strontium-isotope stratigraphy of deep-sea sections.

Large variations exist between published mid-Cretaceous (late Barremian to early Turonian stages) seawater Sr-isotope stratigraphies; this has resulted in disparate interpretations of crustal production rates. We report on a detailed investigation of seawater Sr-isotope stratigraphy based on foraminifers and, where available, on inoceramid bivalves from 12 mid-Cretaceous Deep Sea Drilling Project and Ocean Drilling Program sections. The effects of diagenesis are assessed using scanning electron microscope observations and traceelemental analyses, but are best distinguished by comparing the 87 Sr/ 86 Sr values of similarage samples from different sites. Strontiumisotope analyses compiled from 9 of 12 sites that have detailed age control define one band of common values. This band is used as a composite curve, which presumably represents seawater 87 Sr/ 86 Sr values. The composite curve shows a “trough” of markedly lower 87 Sr/ 86 Sr values in the Aptian and early Albian stages, higher but constant values for the middle Albian-Cenomanian stages, followed by a decrease in 87 Sr/ 86 Sr values in the early Turonian.

Mid-Pliocene sea level and continental ice volume based on coupled benthic Mg/Ca palaeotemperatures and oxygen isotopes

Ostracode magnesium/calcium (Mg/Ca)-based bottom-water temperatures were combined with benthic foraminiferal oxygen isotopes in order to quantify the oxygen isotopic composition of seawater, and estimate continental ice volume and sea-level variability during the Mid-Pliocene warm period, ca 3.3–3.0 Ma. Results indicate that, following a low stand of approximately 65 m below present at marine isotope stage (MIS) M2 (ca 3.3 Ma), sea level generally fluctuated by 20–30 m above and below a mean value similar to present-day sea level. In addition to the low-stand event at MIS M2, significant low stands occurred at MIS KM2 (−40 m), G22 (−40 m) and G16 (−60 m). Six high stands of +10 m or more above present day were also observed; four events (+10, +25,+15 and +30 m) from MIS M1 to KM3, a high stand of +15 m at MIS K1, and a high stand of +25 m at MIS G17. These results indicate that continental ice volume varied significantly during the Mid-Pliocene warm period and that at times there were considerable reductions of Antarctic ice.

Iodide, Bromide, and Ammonium in Hydraulic Fracturing and Oil and Gas Wastewaters: Environmental Implications

The expansion of unconventional shale gas and hydraulic fracturing has increased the volume of the oil and gas wastewater (OGW) generated in the U.S. Here we demonstrate that OGW from Marcellus and Fayetteville hydraulic fracturing flowback fluids and Appalachian conventional produced waters is characterized by high chloride, bromide, iodide (up to 56 mg/L), and ammonium (up to 420 mg/L). Br/Cl ratios were consistent for all Appalachian brines, which reflect an origin from a common parent brine, while the I/Cl and NH4/Cl ratios varied among brines from different geological formations, reflecting geogenic processes. There were no differences in halides and ammonium concentrations between OGW originating from hydraulic fracturing and conventional oil and gas operations. Analysis of discharged effluents from three brine treatment sites in Pennsylvania and a spill site in West Virginia show elevated levels of halides (iodide up to 28 mg/L) and ammonium (12 to 106 mg/L) that mimic the composition of OGW and mix conservatively in downstream surface waters. Bromide, iodide, and ammonium in surface waters can impact stream ecosystems and promote the formation of toxic brominated-, iodinated-, and nitrogen disinfection byproducts during chlorination at downstream drinking water treatment plants. Our findings indicate that discharge and accidental spills of OGW to waterways pose risks to both human health and the environment.

Deep-sea ostracode species diversity: response to late Quaternary climate change

Late Quaternary ostracode assemblages from the North Atlantic Ocean were studied to establish the effect of climatic changes of the past 210,000 yr (marine oxygen isotope stages 7‐1) on deep-sea benthic biodiversity and faunal composition. Two-hundred and twenty five samples from theChain 82-24 Core 4PC (41o43 0 N, 32o51 0 W, 3427 m water depth) on the western Mid-Atlantic Ridge revealed high amplitude fluctuations in ostracode abundance and diversity coincident with orbital and suborbital scale climate oscillations measured by several paleoceanographic proxy records. During the past 210,000 yr, ostracode biodiversity as measured by species number (S) and the Shannon‐Weaver index, H.S/, oscillated from H.S/D 0:4 during glacial periods (marine isotope stages 6, 5d, 5b, 4, and 2) to H.S/D 1:1 during interglacial and interstadial periods (stages 7, 5e, 5c, 5a, 3 and 1). A total of 23 diversity peaks could be recognized. Eleven of these signify major periods of high diversity [ H.S /> 0:8, SD 10‐21] occurring every 15‐20 ka. Twelve were minor peaks which may represent millennial-scale diversity oscillations. The composition of ostracode assemblages varies with Krithe-dominated assemblages characterizing glacial intervals, and Argilloecia‐Cytheropteroncharacterizing deglacials, and trachyleberid genera (Poseidonamicus, Echinocythereis, Henryhowella, Oxycythereis) abundant during interglacials. Diversity and faunal composition changes can be matched to independent deep-sea paleoceanographic tracers such as benthic foraminiferal carbon isotopes, Krithe trace elements (Mg=Ca ratios), and to North Atlantic region climate records such as Greenland ice cores. When interpreted in light of ostracode species’ ecology, these faunal and diversity patterns provide evidence that deep-sea benthic ecosystems experience significant reorganization in response to climate changes over orbital to millennial timescales. Published by Elsevier Science B.V.

Multiproxy evidence of Holocene climate variability from estuarine sediments, eastern North America

water temperature estimated from ostracode Mg/Ca ratios. The results indicate a much drier early Holocene in which mean paleosalinity was � 28 ppt in the northern bay, falling � 25% to � 20 ppt during the late Holocene. Early Holocene Mg/Ca-derived temperatures varied in a relatively narrow range of 13� to 16� C with a mean temperature of 14.2� C and excursions above 16� C; the late Holocene was on average cooler (mean temperature of 12.8� C). In addition to the large contrast between early and late Holocene regional climate conditions, multidecadal (20–40 years) salinity and temperature variability is an inherent part of the region’s climate during both the early and late Holocene, including the Medieval Warm Period and Little Ice Age. These patterns are similar to those observed during the twentieth century caused by NAO-related processes. Comparison of the midlatitude Chesapeake Bay salinity record with tropical climate records of Intertropical Convergence Zone fluctuations inferred from the Cariaco Basin titanium record suggests an anticorrelation between precipitation in the two regions at both millennial and centennial timescales.

Trace Elements in Marine Ostracodes

Extending the work of Cadot, Kaesler, De Deckker, Chivas, and Correge, we have measured the elemental chemistry of shells of marine ostracodes to evaluate the usefulness of ostracode shell chemistry as a paleoenvironmental proxy. Our work has focused primarily on Mg/Ca, Sr/Ca, and Na/Ca ratios of two common genera: deep-sea genus Krithe and shallow marine/estuarine genus Loxoconcha. We evaluated in vivo effects including genus, species, gender, ontogeny, shell size, intra-shell heterogeneity (Mg), water temperature, and salinity, and post-mortem diagenetic effects including partial dissolution, recrystallization, and shell surface contamination. Analysis of modern (core-top), fossil, and laboratory-raised specimens across a wide range of temperature and salinity conditions confirms earlier work indicating that Krithe and Loxoconcha Mg/Ca ratios are dominantly controlled by water temperature. Sr/Ca and Na/Ca ratios co-vary with temperature in core-top Krithe, but not in cultured Loxoconcha suggesting that the Krithe Sr/Ca and Na/Ca correlation with temperature may be related to another variable that broadly co-varies with temperature. Phylogenetic and ontogenetic effects are also indicated, including different Mg-thermodependence and intra-shell Mg distribution between Krithe and Loxoconcha. Inter-specific effects are suggested for two species of Krithe. Magnesium uptake in eldest juvenile shells seems to be identical to that of adult shells, thus greatly increasing the amount of shell material available for paleoenvironmental studies. No salinity effects were observed. Shell Na/Ca ratios showed a dramatic decrease with increasing dissolution (natural and artificial) in waters that are undersaturated with respect to calcite, whereas Mg/Ca ratios displayed a minor decrease and Sr/Ca ratios showed no change. Of the ratios studied, Mg/Ca offers the most promise for Quaternary marine studies as a paleothermometer. Further calibration studies are needed to better understand the marine ostracode Mg/Ca-paleothermometer.

The Impact of Coal Combustion Residue Effluent on Water Resources: A North Carolina Example

The combustion of coal to generate electricity produces about 130 million tons of coal combustion residues (CCRs) each year in the United States; yet their environmental implications are not well constrained. This study systematically documents the quality of effluents discharged from CCR settling ponds or cooling water at ten sites and the impact on associated waterways in North Carolina, compared to a reference lake. We measured the concentrations of major and trace elements in over 300 samples from CCR effluents, surface water from lakes and rivers at different downstream and upstream points, and pore water extracted from lake sediments. The data show that CCR effluents contain high levels of contaminants that in several cases exceed the U.S. EPA guidelines for drinking water and ecological effects. This investigation demonstrates the quality of receiving waters in North Carolina depends on (1) the ratio between effluent flux and freshwater resource volumes and (2) recycling of trace elements through adsorption on suspended particles and release to deep surface water or pore water in bottom sediments during periods of thermal water stratification and anoxic conditions. The impact of CCRs is long-term, which influences contaminant accumulation and the health of aquatic life in water associated with coal-fired power plants.