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.     

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.     

Influence of a hedge surrounding bottomland on seasonal soil‐water movement

The influence of a hedge surrounding bottomland on soil‐water movement along the hillslope was studied on a plot scale for 28 months. The study was based on the comparison of two transects, one with a hedge, the other without, using mainly a dense grid of tensiometers. The influence of the bottomland hedge was located in the area where tree roots were developed, several metres upslope from the hedge, and could be observed both in the saturated and non‐saturated zone, from May to December. The hedge induced a high rate of soil drying, because of the high evaporative capacity of the trees. We evaluated that water uptake by the hedge during the growing season was at least 100 mm higher than without a hedge. This increased drying rate led to a delayed rewetting of the soils upslope from the hedge in autumn, of about 1 month compared with the situation without a hedge. Several consequences of this delayed rewetting are expected: a delay in the return of subsurface transfer from the hillslope to the riparian zone, a buffering effect of hedges on floods, already observed at the catchment scale, and an increased residence time of pollutants. Copyright © 2003 John Wiley & Sons, Ltd.     

The Oxford Principles

Scientific momentum is increasing behind efforts to develop geoengineering options, but it is widely acknowledged that the challenges of geoengineering are as much political and social as they are technical. Legislators are looking for guidance on the governance of geoengineering research and possible deployment. The Oxford Principles are five high-level principles for geoengineering governance. This article explains their intended function and the core societal values which they attempt to capture. Finally, it proposes a framework for their implementation in a flexible governance architecture through the formulation of technology-specific research protocols.     

Effect of Decadal Changes in Freshwater Flows and Temperature on the Larvae of two Forage Fish Species in Coastal Nurseries of the St. Lawrence Estuary

Since 2002, the abundance of larvae of rainbow smelt (Osmerus mordax) and Atlantic herring (Clupea harengus) has been monitored in July in coastal nurseries (Anse Ste.-Anne (ASA) and Banc de Rivière-du-Loup (BRL)) in the Middle St. Lawrence Estuary (MSLE), Canada. The two species are spatiotemporally segregated, with smelt larvae being more abundant at the upstream, less saline site (ASA) and having an earlier hatching date. Despite these differences, the abundances of both species from 2002 to 2013 were strongly and positively related to the early spring flow of tributaries at the time of larval smelt emergence and weakly and negatively related to sea-surface temperatures in the nurseries. Larval herring abundance was weakly associated with the upstream bottom residual transport flow of the MSLE’s estuarine circulation in June, at the time of their emergence. Larval herring lengths in BRL were positively related to the sum of degree days (SDD) from hatching to sampling, with the greatest length but lowest condition in 2012. The relationship between body lengths of ASA smelt larvae and SDD was dome-shaped, suggesting lower growth than expected in the warmest years, 2006 and 2012. The highest larval abundances were observed in 2008 and 2011, both years with late tributary freshets, high tributary flows in the early spring and moderately warm summer temperatures. In contrast, low abundances occurred in 2006 and 2012, which were years with low spring tributary flows and high summer temperatures. These results suggest that the dynamics of local tributary freshets is a key driver of larval recruitment success for two key forage species in coastal nurseries until summer and support the use of fish larvae as indicators of environmental changes in the MSLE.