Surface phase transformations,surface complexation and solubilities of hydroxyapatite in the absence/presence of Cd(II) and EDTA

The removal of Cd from aqueous solutions by hydroxyapatite (HAP) was investigated with and without EDTA being present. Batch experiments were carried out using synthetic hydroxyapatite with Ca/P 1.57 and a specific surface area of 37.5 m²/g in the pH range 4–9 (25 °C; 0.1 M KNO₃). The surface composition of the solid phases were analysed by X-ray Photoelectron Spectroscopy (XPS). The surface layer of HAP was found to undergo a phase transformation with a (Ca + Cd)/P atomic ratio of 1.4 and the involvement of an ion exchange process (Ca²⁺ ↔ Cd²⁺). The amount of Cd removed from the solution increased with increasing pH, reaching ≈100% at pH 9. In the presence of EDTA Cd removal was reduced due to the formation of [CdEDTA]²⁻ in solution. The solubility of HAP increases in the presence of EDTA at pH values above 5, mainly due to the formation of [CaEDTA]²⁻. In contrast to this, the solubility was found to decrease in the presence of Cd²⁺ and CdEDTA²⁻. Using XPS the formation of a Cd-enriched HAP surface was found, which was interpreted as the formation of a solid solution of the general composition: Ca_8.4-xCd_x(HPO_4)1.6(PO_4)4.4(OH_)0.4${\text{Ca}}_{8.4-x}{\text{Cd}}_x({\text{HPO}}_4{)}_{1.6}({\text{PO}}_4{)}_{4.4}(\text{OH}{)}_{0.4}$.     

Rapid physicochemical changes in the high Arctic Lake Kongressvatn caused by recent climate change

High Arctic lakes are among the most sensitive ecosystems and climate change strongly affects their physical properties, especially water temperature, and mixing processes. To study the effect of recent climate change on such a lake in the Arctic environment, we measured water chemistry and temperature from 2005 to 2010 in Kongressvatn, a crenogenic meromictic lake in Spitsbergen (Svalbard). In addition, we monitored water column temperatures during two consecutive years and compared them to regional air temperature data and physicochemical lake data from 1962 and 1968, two relatively cold years. Summer surface water temperature was highly correlated to air temperature, and both have increased by approximately 2°C since 1962. Temperature monitoring during 2?years showed that the warm summer of 2007 resulted in increased water temperatures even in the stratified, denser hypolimnion. Our water chemistry measurements showed that the chemocline position in 2005?C2010 was ca 12?m deeper than in 1962?C1968, and a second, weaker, chemocline appeared at metalimnetic depths of 7?C15?m. During the study period, the water level decreased by 4?m, and this change accelerated between 2008 and 2010. Our data support the hypothesis that water temperatures and stratification patterns are changing rapidly with air temperature, but changes in the catchment, such as glacial retreat and permafrost melting, may have an even stronger impact on lake properties.     

On the potential impact of harbour seal predation on the cod population in the eastern North Sea

Increasing Scandinavian harbour seal populations during the last decades coincide in time with the collapse of the cod fishery. Assumptions of a causal relationship have led to claims favouring re-introduction of seal hunting. Proposals for ‘adaptive management’ often assume that decimating seal populations will automatically favour the fishery. This argument presupposes seal predation to be sufficiently large to have a measurable impact on the fish population. The potential magnitude of the cod-seal interaction was analysed using data on harbour seal abundance, feeding habits and compiled information on cod life history and cod landing statistics. A size-structured life history matrix for the cod population was applied and the size-specific prey preferences of harbour seals were taken into account. Estimated seal predation was small compared to both the landings by the fishery, and to minimum estimates of the total cod population. Furthermore, since the size classes of cod targeted by seals have low reproductive values, the impact of seal predation on cod production will be further reduced. Our analyses suggest harbour seals have a negligible impact on the cod fishery.     

Economics of climate policy and collective decision making

This paper explores the reasons why economic instruments of climate change are reluctantly applied and stresses the need for interdisciplinary research linking economic theory and empirical testing to deliberative political procedures. It is divided in three parts. The first one recalls the main issues in implementing Cost-Benefit Analysis such as information problems, uncertainties, discounting the future and irreversibilities. The second part shows how these issues can be treated in integrated assessment and techno-economic models and presents a case study, which shows that

• The chosen scenario tends to stabilize atmospheric CO₂ concentration at around 550 ppm in the long run.
• Exclusion of possibility to trade CO₂ emission permits under a cap regime would increase the cost of emission abatement for OECD countries.
• Combining different flexibility instruments might lead to significant gains in the overall cost of climate policy.

The third part presents results of a survey conducted among the main economic and environmental associations in Switzerland. The survey reveals conflicting views on economic instruments. It shows how the social acceptability of these instruments can be improved in taking explicitly into account these opposing views of special interest groups. Therefore, policy scenarios should be selected in combining techno-economic models with empirical studies about their political and normative context.     

The use of video imagery to analyse groundwater and shoreline dynamics on a dissipative beach

Groundwater seepage is known to influence beach erosion and accretion processes. However, field measurements of the variation of the groundwater seepage line (GWSL) and the vertical elevation difference between the GWSL and the shoreline are limited. We developed a methodology to extract the temporal variability of the shoreline and the wet-dry boundary using video imagery, with the overarching aim to examine elevation differences between the wet-dry boundary and the shoreline position in relation to rainfall and wave characteristics, during a tidal cycle. The wet-dry boundary was detected from 10 min time-averaged images collected at Ngaranui Beach, Raglan, New Zealand. An algorithm discriminated between the dry and wet cells using a threshold related to the maximum of the red, green, and blue intensities in Hue-Saturation-Value. Field measurements showed this corresponded to the location where the water table was within 2 cm of the beachface surface. Time stacks and time series of pixels extracted from cross-shore transects in the video imagery, were used to determine the location of the shoreline by manually digitizing the maximum run-up and minimum run-down location for each swash cycle, and averaging the result. In our test data set of 14 days covering a range of wave and rainfall conditions, we found 6 days when the elevation difference between the wet-dry boundary and the shoreline remained approximately constant during the tidal cycle. For these days, the wet-dry boundary corresponded to the upper limit of the swash zone. On the other 8 days, the wet-dry boundary and the shoreline decoupled with falling tide, leading to elevation differences of up to 2.5 m at low tide. Elevation differences between the GWSL and the shoreline at low tide were particularly large when the cumulative rainfall in the preceding month was greater than 200 mm. This research shows that the wet-dry boundary (such as often used in video shoreline-finding algorithms) is related to groundwater seepage on low-sloped, medium to fine sand beaches such as Ngaranui Beach (mean grain size ∼0.27 mm, beach slope ∼1:70) and may not be a good indicator of the position of the shoreline.     

Palaeoenvironmental record of glacial lake evolution during the early Holocene at Sokli,NE Finland

The development of a glacial lake impounded along the retreating, northeastern ice margin of the Fennoscandian Ice Sheet during the last deglaciation and environmental conditions directly following the early Holocene deglaciation have been studied in NE Finland. This so‐called Sokli Ice Lake has been reconstructed previously using topographic and geomorphologic evidence. In this paper a multiproxy approach is employed to study a 3‐m‐thick sediment succession consisting of laminated silts grading into gyttja cored in Lake Loitsana, a remnant of the Sokli Ice Lake. Variations in the sediment and siliceous microfossil records indicate distinct changes in water depth and lake size in the Loitsana basin as the Sokli Ice Lake was drained through various spillways opening up along the retreating ice front. Geochemical data (XRF core‐scanning) show changes in the influence of regional catchment geochemistry (Precambrian crystalline rocks) in the glacial lake drainage area versus local catchment geochemistry (Sokli Carbonatite Massif) within the Lake Loitsana drainage area during the lake evolution. Principal component analysis on the geochemical data further suggests that grain‐size is an additional factor responsible for the variability of the sediment geochemistry record. The trophic state of the lake changed drastically as a result of morphometric eutrophication once the glacial lake developed into Lake Loitsana. The AMS radiocarbon dating on tree birch seeds found in the glaciolacustrine sediment indicates that Lake Loitsana was deglaciated sometime prior to 10 700 cal. a BP showing that tree Betula was present on the deglaciated land surrounding the glacial lake. Although glacial lakes covered large areas of northern Finland during the last deglaciation, only few glaciolacustrine sediment successions have been studied in any detail. Our study shows the potential of these sediments for multiproxy analysis and contributes to the reconstruction of environmental conditions in NE Finland directly following deglaciation in the early Holocene.     

Holocene temperature variations at a high-altitude site in the Eastern Alps: a chironomid record from Schwarzsee ob Sölden, Austria

Few well-dated, quantitative Holocene temperature reconstructions exist from high-altitude sites in the Central Eastern Alps. Here, we present a chironomid-based quantitative reconstruction of mean July air temperatures (T_July) throughout the Holocene for a remote high-mountain lake, Schwarzsee ob Sölden, situated above the treeline at 2796 m a.s.l. in the Austrian Alps. Applying a chironomid-temperature inference model developed from lakes of the Alpine region to a high-resolution chironomid record from the lake provides evidence for early Holocene (ca 10000–8600 cal yr BP) T_July of up to 8.5 °C, i.e. >4 °C above the modern (1977–2006) mean July temperature. The reconstruction reveals the so-called ‘8.2-ka cold event’ centered at ca 8250–8000 cal yr BP with temperatures ca 3 °C below the early-Holocene thermal maximum. Rather warm (ca 6 °C) and productive conditions prevailed during ca 7900–4500 cal yr BP. The chironomid record suggests a climate transition between ca 5200 and 4500 cal yr BP to cooler T_July. A distinct cooling trend is evident from ca 4500 until ca 2500 cal yr BP. Thereafter, the study site experienced its coldest conditions (around 4 °C or less) throughout the rest of the Holocene, with the exception of the warming trend during the late 20th century. Beside other factors, the Northern Hemisphere summer insolation seems to be the major driving force for the long-term trends in T_July at high altitudes in the Eastern Alps. Due to the extreme location of the lake and the limited temperature range represented by the applied calibration data set, the chironomid-based temperature reconstruction fails to track phases of the late-Holocene climatic history with T_July cooler than 4 °C. Further chironomid-based palaeoclimate model and down-core studies are required to address this problem, provide more realistic T_July estimates from undisturbed high-altitude lakes in the Alps, and extract a reliable regional temperature signal.     

The 11-year solar cycle, the Sun's rotation, and the middle stratosphere in winter. Part II: Response of planetary waves

The effect of the 11-year solar cycle on the response of planetary wavenumbers 1 and 2 at 10 and 30 hPa in winter to solar activity oscillations on the time scale of the Sun's rotation (27.2 day) is discussed in terms of statistical spectral analysis. The three oscillations studied are the 27.2 d (period of the Sun's rotation), 25.3 d (periodicity caused by modulation of the 27.2 d stratospheric response by annual atmospheric variation), and 54.4 d (doubled period of the solar rotation). A significant effect of the 11-year solar cycle is found for the 54.4 d periodicity in planetary wavenumber 1, and for the 27.2 and 25.3 d periodicities in planetary wavenumber 2. The effect of the 11-year solar cycle is expressed in the evident differences between the amplitudes of responses of planetary waves at maximum and minimum of the solar cycle: the amplitudes are much larger at high than at low solar activity. The 11-year modulation of planetary wave activity is most pronounced at mid-latitudes, mainly at 40–60°N, where the observed variability of planetary waves is large. The results obtained are in good agreement with results of the recent modeling study by Shindell et al. (Science 284 (1999) 305).     

Grounding‐line dynamics during the last deglaciation of Kveithola,W Barents Sea,as revealed by seabed geomorphology and shallow seismic stratigraphy

A marine geophysical study reveals a complex deglaciation pattern in the Kveithola trough, W Barents Sea. The data set includes multibeam swath bathymetry and sub‐bottom sediment profiler (chirp) data acquired for the whole extent of a palaeo, marine‐terminating ice stream, along with high‐resolution single‐channel seismic data from chosen profiles. The multibeam data show a geomorphic landform assemblage characteristic of ice streams. The results of a combination of seismic and chirp unit stratigraphy reveal that the seabed geomorphology is governed by a deeper‐lying reflector. The reflector dominates surface expressions of several subglacial and ice‐marginal units, each connected to a separate episode of ice‐margin stillstand/advance. Analysis of the combined data set has resulted in a conceptual model of the ice‐stream retreat. The model depicts complex deglaciation of a small, confined ice‐stream system through episodic retreat. It describes the formation of several generations of grounding‐zone systems, characterized by high meltwater discharges and the deposition of fine‐grained grounding‐line fans. The inferred style of grounding‐zone deposition in Kveithola deviates from that of other accounts, and is suggested to be intermediate in the previously described continuum between morainal banks and grounding‐line wedges. The results of this paper have implications for grounding‐zone theory and should be of interest to modellers of grounding‐line dynamics and ice‐stream retreat.     

Marine C reservoir ages for 19th century whales and molluscs from the North Atlantic

In order to compare radiocarbon dates on marine and terrestrial samples the former have to be corrected for a reservoir age. We present reservoir ages from dating 21 whales collected 1860–1901 and recalculating dates of 23 molluscs collected 1857–1926. Most of the whales were caught along the coast of Norway, but one is from France and one from Iceland. We assume the former mainly lived in the North and equatorial Atlantic and in the Norwegian Sea. Whales feed only on pelagic organisms and will provide the reservoir age for the open ocean surface water. However, they travel long distances and will integrate the reservoir ages of the different water masses along their way. Molluscs (dated from Norway, Spitsbergen and Arctic Canada) are stationary and monitor the sea water passing their dwelling site, but some also take up carbon from particulate food or sediment pore water. Coastal water also often contains some continental carbon. We present two different views on how to analyze and interpret the data. Mangerud recommends to use reservoir ages based on a combination of the whale and mollusc dates, i.e. 380±30 and 360±30 yr relative to Intcal04 and British oak, respectively, and a ΔR value of 20±30 for the surface water in the N-Atlantic and Norwegian Sea. Bondevik and Gulliksen maintain that the reservoir age—and ΔR—along the Norwegian coast is latitude dependant, with ΔR-values increasing from −3±22 in the South to 105±24 at Spitsbergen. Whales, reflecting North Atlantic open ocean surface water have lower ΔR (7±11) than most molluscs.