A critical review of three methods used for the measurement of mercury (Hg)-dissolved organic matter stability constants     

Jarrod D. Gasper  George R. Aiken  Joseph N. Ryan 《Applied Geochemistry》2007

Three experimental techniques – ion exchange, liquid–liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE–SPE) – were evaluated as methods for determining conditional stability constants (K) for the binding of mercury (Hg²⁺) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid–liquid extraction method was found to be complicated by the ability of Hg–DOM complexes to partition into the organic phase. The CLE–SPE method was found to be the most suitable of these methods for the measurement of Hg–DOM stability constants. Stability constants for DOM isolates measured using the CLE–SPE method at environmentally relevant Hg:DOM ratios were log K = 25–30 (M⁻¹). These values are consistent with the strong Hg²⁺ binding expected for reduced S-containing binding sites.  相似文献   

Tropical cyclone activity and western North Atlantic stratification over the last millennium: a comparative review with viable connections     

Jonathan D. Woodruff  Ryan L. Sriver  David C. Lund 《第四纪科学杂志》2012,27(4):337-343

Tropical cyclones (TC) are recognized to modify the thermal structure of the upper ocean through the process of vertical mixing. Assessing the role this mixing plays in the overall stratification of the upper ocean is difficult, due to the relatively short and incomplete instrumental record. Proxy records for both TC landfalls and oceanographic stratification are preserved within the geological record and provide insight for how past changes in TC‐induced mixing have potentially affected water column structure prior to the instrumental record. Here we provide the first comparison between previously published paleo‐reconstructions of vertical ocean density and tropical cyclone activity from the western North Atlantic. A prominent lull in TC activity has been observed prior to approximately 1700 CE that extends back several centuries. This interval of low TC activity is shown to be concurrent with the timing of increased ocean stratification near Great Bahama Bank, potentially due in part to reduced TC‐induced mixing. To test whether this relationship is feasible, we present numerical results from a coarse‐resolution ocean general circulation model experiment isolating the effect of TC surface wind forcing on the upper ocean. An anomaly of roughly 0.12 kg m^?3 in vertical stratification occurs above and below the mixed layer for model runs with and without TC mixing. This anomaly is roughly 25% of the entire paleo‐density signal observed just prior to 1700 CE. These results suggest that TC mixing alone cannot completely explain the density anomaly observed prior to 1700 CE, but support TC variability as an important contributor to enhancing oceanic stratification during this interval. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

A Geoarchaeological Study of the Middle and Upper Pleistocene Levels at Canteen Kopje,Northern Cape Province,South Africa     

Matt G. Lotter  Ryan J. Gibbon  Kathleen Kuman  George M. Leader  Tim Forssman  Darryl E. Granger 《Geoarchaeology》2016,31(4):304-323

Canteen Kopje, situated in the Northern Cape Province of South Africa, has two main archaeological deposits: alluvial gravels and a mantle of overlying fine sediments known locally as the “Hutton Sands.” This paper focuses on the fine sediments, the three industries contained within them, and the interface with the underlying gravels in an attempt to clarify their formation and transformation. A Fauresmith assemblage is found at this interface; it is thus crucial to understand the processes of deposition and modification at this poorly understood boundary. The methods used in this study involved the analysis of artifact depositional (dip and orientation) and spatial data, artifact condition, raw materials, and assemblage size profiles. Data presented document the mixing between the lowest levels of the fine sediments and the underlying alluvial gravels. This study thus provides important contextual information for the Fauresmith industry at Canteen Kopje.  相似文献   

Habitat selection and quality for multiple cohorts of young-of-the-year bluefish (Pomatomus saltatrix): Comparisons between estuarine and ocean beaches in southern New Jersey   总被引：1，自引：0，他引：1  

David L. Taylor  Ryan S. Nichols  Kenneth W. Able 《Estuarine, Coastal and Shelf Science》2007,73(3-4):667-679

In this study, seasonal and annual variability in the use of estuarine and ocean beaches by young-of-the-year bluefish, Pomatomus saltatrix, was evaluated by indices of abundance in coastal areas of southern New Jersey (1998–2000). Biological and physical factors measured at specific sites were correlated with bluefish abundance to determine the mechanisms underlying habitat selection. In addition, integrative and discrete indicators of bluefish growth were used to examine spatio-temporal dynamics in habitat quality and its effect on habitat selection by multiple cohorts of bluefish. Intra-annual recruitment to coastal areas of southern New Jersey was episodic, and resulted from the ingress of spring-spawned bluefish (hatch-date April) to estuarine beaches in late May to early June, followed by the recruitment of summer-spawned fish (hatch-date early July) to ocean beaches from July to October. Bluefish utilized estuarine and ocean beaches in a facultative manner that was responsive to dynamics in prey composition and temperature conditions. The recruitment and residency of bluefish in the estuary (1998–1999) and ocean beaches (1998), for example, was coincidental with the presence of the Atlantic silverside Menidia menidia and bay anchovy Anchoa mitchilli, the principal prey species for bluefish occupying these respective habitat-types. Bluefish abundance in the estuary (2000) and ocean beaches (1999–2000) was also correlated with water temperature, with the greatest catches of juveniles coinciding with their optimal growth temperature (24 °C). Bluefish growth, estimated as the slope of age–length relationships and daily specific growth rates, equaled 1.27–2.63 mm fork length (FL) d⁻¹ and 3.8–8.7% body length increase d⁻¹, respectively. The growth of sagittal otoliths was also used as a proxy for changes in bluefish size during and shortly before their time of capture. Accordingly, otolith growth rates of summer-spawned bluefish were greater at ocean beaches relative to the estuary and were explained by the more suitable temperature conditions found at ocean beaches during the mid- to late summer. Notwithstanding the fast growth of oceanic summer-spawned bluefish, individuals spawned in the spring were still larger in absolute body size at the end of the summer growing season (240 and 50–200 mm FL for spring- and summer-spawned bluefish, respectively). The size discrepancy between spring- and summer-spawned bluefish at the onset of autumn migrations and during overwintering periods may account for the differential recruitment success of the respective cohorts.  相似文献   

On the origin of impact glass in the Apollo 16 regolith     

Randy L. Korotev  Ryan A. Zeigler  Christine Floss 《Geochimica et cosmochimica acta》2010,74(24):7362-7388

This study addresses the issue of what fraction of the impact glass in the regolith of a lunar landing site derives from local impacts (those within a few kilometers of the site) as opposed to distant impacts (10 or more kilometers away). Among 10,323 fragments from the 64-210-μm grain-size fraction of three Apollo 16 regolith samples, 14% are impact glasses, that is, fragments consisting wholly or largely of glass produced in a crater-forming impact. Another 16% are agglutinates formed by impacts of micrometeorites into regolith. We analyzed the glass in 1559 fragments for major- and minor-element concentrations by electron probe microanalysis and a subset of 112 of the fragments that are homogeneous impact glasses for trace elements by secondary ion mass spectrometry. Of the impact glasses, 75% are substantially different in composition from either the Apollo 16 regolith or any mixture of rocks of which the regolith is mainly composed. About 40% of the impact glasses are richer in Fe, Mg, and Ti, as well as K, P, and Sm, than are common rocks of the feldspathic highlands. These glasses must originate from craters in maria or the Procellarum KREEP Terrane. Of the feldspathic impact glasses, some are substantially more magnesian (greater MgO/FeO) or have substantially lower concentrations of incompatible elements than the regolith of the Apollo 16 site. Many of these, however, are in the range of feldspathic lunar meteorites, most of which derive from points in the feldspathic highlands distant from the Procellarum KREEP Terrane. These observations indicate that a significant proportion of the impact glass in the Apollo 16 regolith is from craters occurring 100 km or more from the landing site. In contrast, the composition of glass in agglutinates, on average, is similar to the composition of the Apollo 16 regolith, consistent with local origin.  相似文献   

Assessing the response of watersheds to catastrophic (logging) and possible secular (global temperature change) perturbations using sediment-chemical chronologies     

David T. Long  Matthew J. Parsons  Catherine H. Yansa  Sharon S. Yohn  Colleen E. McLean  Ryan G. Vannier 《Applied Geochemistry》2010

Geochemical profiles of sediment cores from two oligotrophic lakes (Elk and Mullett) in northern Lower Michigan were studied to examine the response and recovery of watersheds to large-scale logging that occurred between 1850 and 1920. Specific questions addressed were: can the impact of extensive clear-cutting of forests be recognized in the sediment-chemical chronologies, can states of system stability be identified prior to the logging, and are there indications that the systems are recovering and possibly returning to a stable state? To answer these questions, elements were put into four groups as proxies for watershed runoff or export (e.g., Al, Mg), pollution (e.g., Pb, Cu), redox (e.g., Fe, As), and productivity (e.g., Ca, P). It was observed that vertical patterns of all proxies were influenced by logging and the early increases in concentration of pollution proxies were due to increased watershed export, not pollution. System stability might be recognized by relatively symmetrical vertical patterns among all of the proxies or secular changes of slowly increasing or decreasing vertical concentration trajectories. Some pre-logging trajectories were punctuated by episodes of slightly elevated concentrations that appear to be related to comparatively warmer periods during the Little Ice Age. Iron and Mn enrichments caused by increased watershed runoff might be misinterpreted as paleo-redox horizons. Results are interpreted to indicate that (1) reference conditions may be better defined as the temporal trends among proxy groups and not individual concentrations, (2) simply assuming pre-1800 conditions as a reference may not be appropriate, (3) inter-proxy group comparisons are needed to help for interpretations of intra-proxy group patterns, (4) the possible regime shift identified here might be expected for other ecosystems because of the intensity of human disturbances and secular changes, and (5) without consideration of a possible regime shift, recovery from logging is estimated to be on the order of 75–130 a, but shorter if regime shifts are considered.  相似文献   

Estimating present day extreme water level exceedance probabilities around the coastline of Australia: tropical cyclone-induced storm surges   总被引：2，自引：0，他引：2  

Ivan D. Haigh  Leigh R. MacPherson  Matthew S. Mason  E. M. S. Wijeratne  Charitha B. Pattiaratchi  Ryan P. Crompton  Steve George 《Climate Dynamics》2014,42(1-2):139-157

The incidence of major storm surges in the last decade have dramatically emphasized the immense destructive capabilities of extreme water level events, particularly when driven by severe tropical cyclones. Given this risk, it is vitally important that the exceedance probabilities of extreme water levels are accurately evaluated to inform risk-based flood and erosion management, engineering and for future land-use planning and to ensure the risk of catastrophic structural failures due to under-design or expensive wastes due to over-design are minimised. Australia has a long history of coastal flooding from tropical cyclones. Using a novel integration of two modeling techniques, this paper provides the first estimates of present day extreme water level exceedance probabilities around the whole coastline of Australia, and the first estimates that combine the influence of astronomical tides, storm surges generated by both extra-tropical and tropical cyclones, and seasonal and inter-annual variations in mean sea level. Initially, an analysis of tide gauge records has been used to assess the characteristics of tropical cyclone-induced surges around Australia. However, given the dearth (temporal and spatial) of information around much of the coastline, and therefore the inability of these gauge records to adequately describe the regional climatology, an observationally based stochastic tropical cyclone model has been developed to synthetically extend the tropical cyclone record to 10,000 years. Wind and pressure fields derived for these synthetically generated events have then been used to drive a hydrodynamic model of the Australian continental shelf region with annual maximum water levels extracted to estimate exceedance probabilities around the coastline. To validate this methodology, selected historic storm surge events have been simulated and resultant storm surges compared with gauge records. Tropical cyclone induced exceedance probabilities have been combined with estimates derived from a 61-year water level hindcast described in a companion paper to give a single estimate of present day extreme water level probabilities around the whole coastline of Australia. Results of this work are freely available to coastal engineers, managers and researchers via a web-based tool (www.sealevelrise.info). The described methodology could be applied to other regions of the world, like the US east coast, that are subject to both extra-tropical and tropical cyclones.  相似文献   

Critical mechanisms for the formation of extreme arctic sea-ice extent in the summers of 2007 and 1996     

Xiquan Dong  Behnjamin J. Zib  Baike Xi  Ryan Stanfield  Yi Deng  Xiangdong Zhang  Bing Lin  Charles N. Long 《Climate Dynamics》2014,43(1-2):53-70

Along with significant changes in the Arctic climate system, the largest year-to-year variation in sea-ice extent (SIE) has occurred in the Laptev, East Siberian, and Chukchi seas (defined here as the area of focus, AOF), among which the two highly contrasting extreme events were observed in the summers of 2007 and 1996 during the period 1979–2012. Although most efforts have been devoted to understanding the 2007 low, a contrasting high September SIE in 1996 might share some related but opposing forcing mechanisms. In this study, we investigate the mechanisms for the formation of these two extremes and quantitatively estimate the cloud-radiation-water vapor feedback to the sea-ice-concentration (SIC) variation utilizing satellite-observed sea-ice products and the NASA MERRA reanalysis. The low SIE in 2007 was associated with a persistent anticyclone over the Beaufort Sea coupled with low pressure over Eurasia, which induced anomalous southerly winds. Ample warm and moist air from the North Pacific was transported to the AOF and resulted in positive anomalies of cloud fraction (CF), precipitable water vapor (PWV), surface LWnet (down-up), total surface energy and temperature. In contrast, the high SIE event in 1996 was associated with a persistent low pressure over the central Arctic coupled with high pressure along the Eastern Arctic coasts, which generated anomalous northerly winds and resulted in negative anomalies of above mentioned atmospheric parameters. In addition to their immediate impacts on sea ice reduction, CF, PWV and radiation can interplay to lead to a positive feedback loop among them, which plays a critical role in reinforcing sea ice to a great low value in 2007. During the summer of 2007, the minimum SIC is 31 % below the climatic mean, while the maximum CF, LWnet and PWV can be up to 15 %, 20 Wm^?2, and 4 kg m^?3 above. The high anti-correlations (?0.79, ?0.61, ?0.61) between the SIC and CF, PWV, and LWnet indicate that CF, PWV and LW radiation are indeed having significant impacts on the SIC variation. A new record low occurred in the summer of 2012 was mainly triggered by a super storm over the central Arctic Ocean in early August that caused substantial mechanical ice deformation on top of the long-term thinning of an Arctic ice pack that had become more dominated by seasonal ice.  相似文献   

The influence of irrigation and Wuliangsuhai Lake on groundwater quality in eastern Hetao Basin,Inner Mongolia,China     

Dongnan Zhu  M. Cathryn Ryan  Biao Sun  Changyou Li 《Hydrogeology Journal》2014,22(5):1101-1114

Geochemical and isotopic characterization of groundwater and lake-water samples were combined with water and total dissolved solids balances to evaluate sources of groundwater quality deterioration in eastern Hetao Basin, Inner Mongolia, China. Groundwater quality is poor; 11 of 13 wells exceed drinking-water guidelines for at least one health-based parameter and all wells exceed aesthetic guidelines. The well water is largely derived from Yellow River irrigation water. Notably high uranium concentrations in the Yellow River, relative to world rivers, suggest groundwater uranium and other trace elements may originate in the river-derived irrigation water. Complex hydrostratigraphy and spatial variation in groundwater recharge result in spatially complex groundwater flow and geochemistry. Evapotranspiration of irrigation water causes chloride concentration increases of up to two orders of magnitude in the basin, notably in shallow groundwater around Wuliangsuhai Lake. In addition to evapotranspiration, groundwater quality is affected by mineral precipitation and dissolution, silicate weathering, and redox processes. The lake-water and TDS balances suggest that a small amount of discharge to groundwater (but associated with very high solute concentrations) contributes to groundwater salinization in this region. Increasing salinity in the groundwater and Wuliangsuhai Lake will continue to deteriorate water quality unless irrigation management practices improve.  相似文献   

Density-Stratified Flow Events in Great Salt Lake,Utah, USA: Implications for Mercury and Salinity Cycling     

David L. Naftz  Gregory T. Carling  Cory Angeroth  Michael Freeman  Ryan Rowland  Eddy Pazmiño 《Aquatic Geochemistry》2014,20(6):547-571

Density stratification in saline and hypersaline water bodies from throughout the world can have large impacts on the internal cycling and loading of salinity, nutrients, and trace elements. High temporal resolution hydroacoustic and physical/chemical data were collected at two sites in Great Salt Lake (GSL), a saline lake in the western USA, to understand how density stratification may influence salinity and mercury (Hg) distributions. The first study site was in a causeway breach where saline water from GSL exchanges with less saline water from a flow restricted bay. Near-surface-specific conductance values measured in water at the breach displayed a good relationship with both flow and wind direction. No diurnal variations in the concentration of dissolved (<0.45 μm) methylmercury (MeHg) were observed during the 24-h sampling period; however, the highest proportion of particulate Hg_total and MeHg loadings was observed during periods of elevated salinity. The second study site was located on the bottom of GSL where movement of a high-salinity water layer, referred to as the deep brine layer (DBL), is restricted to a naturally occurring 1.5-km-wide “spillway” structure. During selected time periods in April/May, 2012, wind-induced flow reversals in a railroad causeway breach, separating Gunnison and Gilbert Bays, were coupled with high-velocity flow pulses (up to 55 cm/s) in the DBL at the spillway site. These flow pulses were likely driven by a pressure response of highly saline water from Gunnison Bay flowing into the north basin of Gilbert Bay. Short-term flow reversal events measured at the railroad causeway breach have the ability to move measurable amounts of salt and Hg from Gunnison Bay into the DBL. Future disturbance to the steady state conditions currently imposed by the railroad causeway infrastructure could result in changes to the existing chemical balance between Gunnison and Gilbert Bays. Monitoring instruments were installed at six additional sites in the DBL during October 2012 to assess impacts from any future modifications to the railroad causeway.  相似文献