Tree height strongly affects estimates of water-use efficiency responses to climate and CO2 using isotopes.

Various studies report substantial increases in intrinsic water-use efficiency (W i ), estimated using carbon isotopes in tree rings, suggesting trees are gaining increasingly more carbon per unit water lost due to increases in atmospheric CO2. Usually, reconstructions do not, however, correct for the effect of intrinsic developmental changes in W i as trees grow larger. Here we show, by comparing W i across varying tree sizes at one CO2 level, that ignoring such developmental effects can severely affect inferences of trees' W i . W i doubled or even tripled over a trees' lifespan in three broadleaf species due to changes in tree height and light availability alone, and there are also weak trends for Pine trees. Developmental trends in broadleaf species are as large as the trends previously assigned to CO2 and climate. Credible future tree ring isotope studies require explicit accounting for species-specific developmental effects before CO2 and climate effects are inferred.Intrinsic water-use efficiency (W i ) reconstructions using tree rings often disregard developmental changes in W i as trees age. Here, the authors compare W i across varying tree sizes at a fixed CO2 level and show that ignoring developmental changes impacts conclusions on trees' W i responses to CO2 or climate.

Changes in cerebral oxygen saturation and haemoglobin concentration during paediatric cardiac surgery.

Although near-infrared spectroscopy (NIRS) enables bedside assessment of cerebral oxygenation, it provides little information on the cause of deoxygenation. The authors aimed to investigate the changes in cerebral oxygenation and haemoglobin concentration and their associations during paediatric cardiac surgery in order to elucidate the physiology underlying cerebral deoxygenation. An observational retrospective study on 399 patients who underwent paediatric cardiac surgery was conducted. With use of NIRS, cerebral oxygen saturation as expressed by tissue oxygen index (TOI) before and after surgery, concentration changes in oxygenated haemoglobin (Δ[HbO2]) and deoxygenated haemoglobin (Δ[HHb]) after surgery were studied as were the associations between these values and clinical variables. TOI decreased after surgery (preoperative versus postoperative value, 66.0% [56.9, 71.3] versus 63.2% [54.3, 69.4], median [25th, 75th percentile], P <0.001) and the decrease was greater in higher category groups in the Risk Adjusted Classification for Congenital Heart Surgery (RACHS-1). [HHb] increased from its baseline (+1.74 µmol/l [-1.57, +5.84], P <0.001) and the increase was greater in higher risk category groups. On the contrary, there was no evidence for a change in [HbO2] (+0.45 µmol/l [-4.76, +5.30], P=0.42). Cerebral oxygen saturation decreased after paediatric cardiac surgery and the decrease was greater in patients of higher risk groups. The increase in [HHb] was considered to play a predominant role in the cerebral deoxygenation noted, in particular in higher RACHS-1 category groups.

Bacterially mediated removal of phosphorus and cycling of nitrate and sulfate in the waste stream of a "zero-discharge" recirculating mariculture system.

Simultaneous removal of nitrogen and phosphorus by microbial biofilters has been used in a variety of water treatment systems including treatment systems in aquaculture. In this study, phosphorus, nitrate and sulfate cycling in the anaerobic loop of a zero-discharge, recirculating mariculture system was investigated using detailed geochemical measurements in the sludge layer of the digestion basin. High concentrations of nitrate and sulfate, circulating in the overlying water (∼15 mM), were removed by microbial respiration in the sludge resulting in a sulfide accumulation of up to 3 mM. Modelling of the observed S and O isotopic ratios in the surface sludge suggested that, with time, major respiration processes shifted from heterotrophic nitrate and sulfate reduction to autotrophic nitrate reduction. The much higher inorganic P content of the sludge relative to the fish feces is attributed to conversion of organic P to authigenic apatite. This conclusion is supported by: (a) X-ray diffraction analyses, which pointed to an accumulation of a calcium phosphate mineral phase that was different from P phases found in the feces, (b) the calculation that the pore waters of the sludge were highly oversaturated with respect to hydroxyapatite (saturation index = 4.87) and (c) there was a decrease in phosphate (and in the Ca/Na molar ratio) in the pore waters simultaneous with an increase in ammonia showing there had to be an additional P removal process at the same time as the heterotrophic breakdown of organic matter.

A comparison study of haemolysis production in three contemporary centrifugal pumps.

One challenge in providing extracorporeal circulation is to supply optimal flow while minimising adverse effects, such as haemolysis. To determine if the recent generation constrained vortex pumps with their inherent design improvements would lead to reduced red cell trauma, we undertook a study comparing three devices. Utilizing a simulated short-term ventricular assist circuit primed with whole human blood, we examined changes in plasma free haemoglobin values over a six-day period. The three pumps investigated were the Maquet Rotaflow, the Levitronix PediVAS and the Medos Deltastream DP3.This study demonstrated that all three pumps produced low levels of haemolysis and are suitable for use in a clinical environment. The Levitronix PediVAS was significantly less haemolytic than either the Rotaflow (p<0.05) or the DP3 (p<0.05). There was no significant difference in plasma free haemoglobin between the Rotaflow and the DP3 (p=0.71).

The importance of the relationship between scale and process in understanding long-term DOC dynamics.

Concentrations of dissolved organic carbon have increased in many, but not all, surface waters across acid impacted areas of Europe and North America over the last two decades. Over the last eight years several hypotheses have been put forward to explain these increases, but none are yet accepted universally. Research in this area appears to have reached a stalemate between those favouring declining atmospheric deposition, climate change or land management as the key driver of long-term DOC trends. While it is clear that many of these factors influence DOC dynamics in soil and stream waters, their effect varies over different temporal and spatial scales. We argue that regional differences in acid deposition loading may account for the apparent discrepancies between studies. DOC has shown strong monotonic increases in areas which have experienced strong downward trends in pollutant sulphur and/or seasalt deposition. Elsewhere climatic factors, that strongly influence seasonality, have also dominated inter-annual variability, and here long-term monotonic DOC trends are often difficult to detect. Furthermore, in areas receiving similar acid loadings, different catchment characteristics could have affected the site specific sensitivity to changes in acidity and therefore the magnitude of DOC release in response to changes in sulphur deposition. We suggest that confusion over these temporal and spatial scales of investigation has contributed unnecessarily to the disagreement over the main regional driver(s) of DOC trends, and that the data behind the majority of these studies is more compatible than is often conveyed.

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer.

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer.

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.

Denitrification and phenol degradation in a contaminated aquifer.

A natural groundwater system modified by pollutant phenols and agricultural nitrate has been modelled in the laboratory by a series of sacrificial microcosm experiments. Samples of aquifer sediment and groundwater from the margin of the phenol plume were used to inoculate anaerobic microcosms enriched in nitrate and pollutant phenols. Rapid degradation of phenol and p-cresol was observed over a 35-day period leading to the generation of inorganic carbon and a number of transient intermediates. O-cresol proved to be recalcitrant on the experimental time-scale. A mass balance calculation shows that, during degradation, carbon was conserved in the aqueous phase. Groundwater-sediment interactions were monitored using carbon stable isotope data. A mass balance for solution TIC indicates thatp-cresol degradation stimulated the dissolution of sedimentary carbonate phases due to the formation of carbonic acid. Compound-specific carbon isotope analysis (GC-IRMS) was used to search for 13C enrichment in residual p-cresol. A slight enrichment trend (epsilon = -2.5/1000) was tentatively identified. The potential of this fractionation effect for obtaining in situ degradation rates is discussed. Results from the microcosm experiments help to explain the observed distribution of nitrate and phenols within the polluted aquifer.

Sulphur isotopic investigation of a polluted raised bog and the uptake of pollutant sulphur by Sphagnum.

The sulphur content and sulphur isotopic composition of Sphagnum as well as anionic compositions and sulphur isotope ratios of rainwater inputs and bog waters have been measured at Thorne Moors, a raised bog in eastern England. Rainwater sulphate isotopic composition shows the sulphur input at this site to be dominated by anthropogenic pollution from fossil fuel burning. Strong depletion of sulphate (low SO4(2-)/Cl-) and enrichment in 34S in sulphate occurs at depth in the bog porewaters due to bacterial sulphate reduction. Some surface waters have low SO4(2-)/Cl-) and are 34S enriched due to removal of sulphate by downward diffusion into a sulphate-reducing zone. Other sites have high SO4(2-)/Cl-) which appears to result from oxidation of organically bound sulphur in the peat. Sulphur is present in Sphagnum at around 0.2% by weight and is depleted by 0 to -9 per thousand in the heavier 34S isotope compared to sulphate. Comparison with similar data from pristine coastal sites shows that sulphur incorporation into Sphagnum is enhanced in the polluted site (as Sphagnum sulphur concentrations are higher at lower total sulphur inputs) and that sulphur incorporation is accompanied by a smaller isotopic shift than in the pristine sites. The data support a model of preferential incorporation of partially reduced sulphur species (probably HSO3-) into Sphagnum. In pristine sites these are only available as oxidation products of sulphide formed by sulphate reduction and are 32S depleted. In polluted sites this source is augmented by sulphur(IV) species in atmospheric inputs and the resultant mixture is less depleted in 32S. Thus, in the polluted sites more HSO3- is available for uptake and the isotopic shift between Sphagnum and aqueous sulphur species is smaller.

Organic carbon concentration profiles in recent cave sediments: records of agricultural pollution or diagenesis?

Recent (<7 years old) cave sediments in Speedwell Cavern, Derbyshire, show an approximately exponential decay of organic carbon with depth. This phenomenon was thought to be due to one of two causes: (i) changing agricultural practice within the catchment feeding the cave, especially the increased use of sewage sludge and animal slurry as fertilizer; (ii) a relatively constant organic carbon concentration over time in the input sediment, with subsequent carbon mineralization during diagenesis. Carbon isotope composition of the organic material and the evolution of H/C ratio with depth indicate that the latter hypothesis is correct and that the profiles result from microbial diagenesis, not increased organic carbon inputs. By comparison with sediment of known (7 years) age, temporal decay constants for organic matter can be derived; these lie between rates previously determined for organic matter decomposition in marine sediments and soils. The H/C ratio of organic matter can be modelled as a function of time and proceeds in a similar fashion to soil organic material.

Redistribution of uranium by physical processes during weathering and implications for radon production.

Erosion of the Edale shales of Derbyshire during the Tertiary and Quaternary has resulted in sediment deposits in and on the underlying karstified limestones. Sorting during sedimentation has generated clay-rich sediments which are uranium enriched due to a clay association of uranium in the shales. Radon production in these sediments is at or close to equilibrium with their uranium content, and their fine grain-size ensures efficient radon release. Such sediments are therefore potent local sources of environmental radon.

The disposal of flue gas desulphurisation waste: sulphur gas emissions and their control.

Flue gas desulphurisation (FGD) equipment to be fitted to UK coal-fired power stations will produce more than 0.8 Mtonnes of calcium sulphate, as gypsum. Most gypsum should be of commercial quality, but any low grade material disposed as waste has the potential to generate a range of sulphur gases, including H2S, COS, CS2, DMS and DMDS. Literature data from the USA indicates that well-oxidised waste with a high proportion of calcium sulphate (the main UK product of FGD) has relatively low emissions of sulphur gases, which are comparable to background levels from inland soils. However, sulphur gas fluxes are greatly enhanced where reducing conditions become established within the waste, hence disposal strategies should be formulated to prevent the sub-surface consumption of oxygen.