The dissociation constants of carbonic acid in seawater at salinities 5 to 45 and temperatures 0 to 45°C

The pK₁^* and pK₂^* for the dissociation of carbonic acid in seawater have been determined from 0 to 45°C and S = 5 to 45. The values of pK₁^* have been determined from emf measurements for the cell:

Pt](1 − X)H2 + XCO2|NaHCO3, CO2 in synthetic seawater|AgC1; Ag

where X is the mole fraction of CO₂ in the gas. The values of pK₂^* have been determined from emf measurements on the cell:

Pt, H2(g, 1 atm)|Na2CO3, NaHCO3 in synthethic seawater|AgC1; Ag

The results have been fitted to the equations:

lnK^*₁ = 2.83655 − 2307.1266/T − 1.5529413 lnT + (−0.20760841 − 4.0484/T)S^0.5 + 0.08468345S − 0.00654208S¹

InK^*₂ = −9.226508 − 3351.6106/T− 0.2005743 lnT + (−0.106901773 − 23.9722/T)S^0.5 + 0.1130822S − 0.00846934S^1.5

where T is the temperature in K, S is the salinity, and the standard deviations of the fits are σ = 0.0048 in lnK₁^* and σ = 0.0070 in lnK₂^*.Our new results are in good agreement at S = 35 (±0.002 in pK₁^*and ±0.005 in pK₂^*) from 0 to 45°C with the earlier results of Goyet and Poisson (1989). Since our measurements are more precise than the earlier measurements due to the use of the Pt, H₂|AgCl, Ag electrode system, we feel that our equations should be used to calculate the components of the carbonate system in seawater.     

Public health impacts of climate change in Washington State: projected mortality risks due to heat events and air pollution

Illness and mortality related to heat and worsening air quality are core public health concerns associated with climate change projections. We examined the historical relationship between age- and cause-specific mortality rates from 1980 through 2006 and heat events at the 99th percentile of humidex values in the historic period from January 1, 1970 to December 31, 2006 in the greater Seattle area (King, Pierce and Snohomish counties), Spokane County, the Tri-Cities (Benton and Franklin counties) and Yakima County; the relative risks of mortality during heat events were applied to population and climate projections for Washington State to calculate number of deaths above the baseline (1980–2006) expected during projected heat events in 2025, 2045 and 2085. Three different warming scenarios were used in the analysis. Relative risks for the greater Seattle area showed a significant dose-response relationship between heat event duration and daily mortality rates for non-traumatic deaths for persons ages 45 and above, typically peaking at four days of exposure to humidex values above the 99th percentile. The largest number of projected excess deaths in all years and scenarios for the Seattle region was found for age 65 and above. Under the middle warming scenario, this age group is expected to have 96, 148 and 266 excess deaths from all non-traumatic causes in 2025, 2045 and 2085, respectively. We also examined projected excess deaths due to ground-level ozone concentrations at mid century (2045–2054) in King and Spokane counties. Current (1997–2006) ozone measurements and mid-twenty-first century ozone projections were coupled with dose-response data from the scientific literature to produce estimates overall and cardiopulmonary mortality. Daily maximum 8-h ozone concentrations are forecasted to be 16–28% higher in the mid twenty-first century compared to the recent decade of 1997–2006. By mid-century in King County the non-traumatic mortality rate related to ozone was projected to increase from baseline (0.026 per 100,000; 95% confidence interval 0.013–0.038) to 0.033 (95% CI 0.017–0.049). For the same health outcome in Spokane County, the baseline period rate of 0.058 (95% CI 0.030–0.085) was estimated increase to 0.068 (95% CI 0.035–0.100) by mid-century. The cardiopulmonary death rate per 100,000 due to ozone was estimated to increase from 0.011 (95% CI 0.005–0.017) to 0.015 (0.007–0.022) in King County, and from 0.027 (95% CI 0.013–0.042) to 0.032 (95% CI 0.015–0.049) in Spokane County. Public health interventions aimed at protecting Washington’s population from excessive heat and increased ozone concentrations will become increasingly important for preventing deaths, especially among older adults. Furthermore, heat and air quality related illnesses that do not result in death, but are serious nevertheless, may be reduced by the same measures.     

The iron-nickel-phosphorus system: Effects on the distribution of trace elements during the evolution of iron meteorites

To better understand the partitioning behavior of elements during the formation and evolution of iron meteorites, two sets of experiments were conducted at 1 atm in the Fe-Ni-P system. The first set examined the effect of P on solid metal/liquid metal partitioning behavior of 22 elements, while the other set explored the effect of the crystal structures of body-centered cubic (α)- and face-centered cubic (γ)-solid Fe alloys on partitioning behavior. Overall, the effect of P on the partition coefficients for the majority of the elements was minimal. As, Au, Ga, Ge, Ir, Os, Pt, Re, and Sb showed slightly increasing partition coefficients with increasing P-content of the metallic liquid. Co, Cu, Pd, and Sn showed constant partition coefficients. Rh, Ru, W, and Mo showed phosphorophile (P-loving) tendencies. Parameterization models were applied to solid metal/liquid metal results for 12 elements. As, Au, Pt, and Re failed to match previous parameterization models, requiring the determination of separate parameters for the Fe-Ni-S and Fe-Ni-P systems.Experiments with coexisting α and γ Fe alloy solids produced partitioning ratios close to unity, indicating that an α versus γ Fe alloy crystal structure has only a minor influence on the partitioning behaviors of the trace element studied. A simple relationship between an element’s natural crystal structure and its α/γ partitioning ratio was not observed. If an iron meteorite crystallizes from a single metallic liquid that contains both S and P, the effect of P on the distribution of elements between the crystallizing solids and the residual liquid will be minor in comparison to the effect of S. This indicates that to a first order, fractional crystallization models of the Fe-Ni-S-P system that do not take into account P are appropriate for interpreting the evolution of iron meteorites if the effects of S are appropriately included in the effort.     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.     

Integration of optical and Synthetic Aperture Radar (SAR) imagery for delivering operational annual crop inventories

Agriculture plays a critical role within Canada’s economy and, as such, sustainability of this sector is of high importance. Targeting and monitoring programs designed to promote economic and environmental sustainability are a vital component within Canada’s agricultural policy. A hierarchy of land information, including up to date information on cropping practices, is needed to measure the impacts of programs on land use decision-making and to gauge the environmental and economic benefits of these investments. A multi-year, multi-site research activity was completed to develop a robust methodology to inventory crops across Canada’s large and diverse agricultural landscapes. To move towards operational implementation the methodology must deliver accurate crop inventories, with consistency and reliability. In order to meet these operational requirements and to mitigate risk associated with reliance on a single data source, the methodology integrated both optical and Synthetic Aperture Radar (SAR) imagery. The results clearly demonstrated that multi-temporal satellite data can successfully classify crops for a variety of cropping systems present across Canada. Overall accuracies of at least 85% were achieved, and most major crops were also classified to this level of accuracy. Although multi-temporal optical data would be the preferred data source for crop classification, a SAR-optical dataset (two Envisat ASAR images and one optical image) provided acceptable accuracies and will mitigate risk associated with operational implementation. The preferred dual-polarization mode would be VV–VH. Not only were these promising classification results repeated year after year, but the target accuracies were met consistently for multiple sites across Canada, all with varying cropping systems.     

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

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.     

Detection of iodine monoxide radicals in the marine boundary layer using laser induced fluorescence spectroscopy

A Laser Induced Fluorescence (LIF) instrument has been developed to detect iodine monoxide (IO) radicals in the atmosphere. An all solid-state Nd:YAG pumped Ti:Sapphire laser operating at approximately 445 nm was used to excite the (2,0) band of the IO A²Π_3/2 ← X²Π_3/2 electronic transition, with off-resonance fluorescence in the (2,5) band detected at 521 nm. The sensitivity of the instrument was determined by calibration. IO (between 10 and 150 pptV) was generated following the 184.9 nm photolysis of N₂O/CF₃I/N₂ mixtures with O₃ actinometry used to determine the photolysis flux. The detection limit was determined to be 0.3 pptV for a 300 s integration period, with an uncertainty of 23% (1σ). The instrument was deployed in August/September 2006 during the RHaMBLe (Reactive Halogens in the Marine Boundary Layer) campaign in Roscoff, France. Located on a small jetty, a few metres from the water’s edge at high tide, the instrument measured significant levels of IO on 11 days, with a maximum of 27.6 ± 3.2 pptV observed on one day (averaged over 10 s) representing the highest IO mixing ratio recorded in the marine boundary layer to date. IO displayed a clear diurnal profile with a maximum at low tide during the daytime. These results represent the first point measurements of IO in the atmosphere by LIF.     

Constraining jet/disc geometry and radiative processes in stellar black holes XTE J1118+480 and GX 339−4

We present results from modelling of quasi-simultaneous broad-band (radio through X-ray) observations of the Galactic stellar black hole (BH) transient X-ray binary (XRB) systems XTE J1118+480 and GX 339−4 using an irradiated disc + compact jet model. In addition to quantifying the physical properties of the jet, we have developed a new irradiated disc model which also constrains the geometry and temperature of the outer accretion disc by assuming a disc heated by viscous energy release and X-ray irradiation from the inner regions. For the source XTE J1118+480, which has better spectral coverage of the two in optical and near-infrared (OIR) wavelengths, we show that the entire broad-band continuum can be well described by an outflow-dominated model + an irradiated disc. The best-fitting radius of the outer edge of the disc is consistent with the Roche lobe geometry of the system, and the temperature of the outer edge of the accretion disc is similar to those found for other XRBs. Irradiation of the disc by the jet is found to be negligible for this source. For GX 339−4, the entire continuum is well described by the jet-dominated model only, with no disc component required. For the two XRBs, which have very different physical and orbital parameters and were in different accretion states during the observations, the sizes of the jet base are similar and both seem to prefer a high fraction of non-thermal electrons in the acceleration/shock region and a magnetically dominated plasma in the jet. These results, along with recent similar results from modelling other galactic XRBs and AGNs, may suggest an inherent unity in diversity in the geometric and radiative properties of compact jets from accreting black holes.