Impacts of climate change scenarios on dissolved oxygen in the River Thames, UK

A water quality model is used to assess the impact of possible climate change on dissolved oxygen (DO) in the Thames. The Thames catchment is densely populated and, typically, many pressures are anthropogenic. However, that same population also relies on the river for potable water supply and as a disposal route for treated wastewater. Thus, future water quality will be highly dependent on future activity. Dynamic and stochastic modelling has been used to assess the likely impacts on DO dynamics along the river system and the probability distributions associated with future variability. The modelling predictions indicate that warmer river temperatures and drought act to reduce dissolved oxygen concentrations in lowland river systems

Effects of different calcium salts on properties of milk related to heat stability

Insoluble calcium salts were added to milk to increase total calcium by 30 mM, without changing properties influencing heat stability, such as pH and ionic calcium. There were no major signs of instability associated with coagulation, sediment formation or fouling when subjected to ultra high temperature (UHT) and in-container sterilisation. The buffering capacity was also unaltered. On the other hand, addition of soluble calcium salts reduced pH, increased ionic calcium and caused coagulation to occur. Calcium chloride showed the largest destabilising effect, followed by calcium lactate and calcium gluconate. Milk became unstable to UHT processing at lower calcium additions compared to in-container sterilisation.

Effect of replacing calcium salts of palm oil distillate with rapeseed oil, milled or whole rapeseeds on milk fatty-acid composition in cows fed maize silage-based diets

Inclusion of rapeseed feeds in dairy cow diets has the potential to reduce milk fat saturated fatty acid (SFA) and increase cis-monounsaturated fatty acid (cis-MUFA) content but effectiveness may depend on the form in which the rapeseed is presented. Four mid-lactation Holstein dairy cows were allocated to four maize silage-based dietary treatments according to a 4 x 4 Latin Square design, with 28-day experimental periods. Treatments consisted of a control diet (C containing 49 g/kg dry matter (DM) of calcium salts of palm oil distillate (CPO), or 49 g/kg DM of oil supplied as whole rapeseeds (WR), rapeseeds milled with wheat (MR) or rapeseed oil (RO). Replacing CPO with rapeseed feeds had no effect (P > 0.05) on milk fat and protein content, while milk yields were higher (P < 0.05) for RO and MR compared with WR (37.1, 38.1 and 34.3 kg/day, respectively). Substituting CPO with RO or MR reduced (P < 0.05) milk fat total SFA content (69.6, 55.6, 71.7 and 61.5 g/100g fatty acids for C, RO, WR and MR, respectively) and enhanced (P < 0.05) milk cis-9 18:1 MUFA concentrations (corresponding values 18.6, 24.3, 17.0 and 23.0 g/100g fatty acids) compared with C and WR. Treatments RO and MR also increased (P < 0.05) milk trans-MUFA content (4.4, 6.8, 10.5 g/100g fatty acids, C MR and RO, respectively). A lack of significant changes in milk fat composition when replacing CPO with WR suggests limited bioavailability of fatty acids in intact rapeseeds. In conclusion, replacing a commercial palm oil-based fat supplement in the diet with milled rapeseeds or rapeseed oil represented an effective strategy to alter milk fatty acid composition with the potential to improve human health. Inclusion of processed rapeseeds offered a good compromise for reducing milk SFA and increasing cis-MUFA, whilst minimising milk trans-MUFA and negative effects on animal performance.

Effect of replacing calcium salts of palm oil distillate with extruded linseeds on milk fatty acid composition in Jersey and Holstein cows

Clinical and biomedical studies have provided evidence for the critical role of n-3 fatty acids on the reduction of chronic disease risk in humans, including cardiovascular disease. In the current experiment, the potential to enhance milk n-3 content in two breeds with inherent genetic differences in mammary lipogenesis and de novo fatty acid synthesis was examined using extruded linseeds. Six lactating cows (three Holstein and three Jersey) were used in a two-treatment switchback design with 3 × 21-day experimental periods to evaluate the effect of iso-energetic replacement of calcium salts of palm oil distillate (CPO) in the diet (34 g/kg dry matter (DM)) with 100 g/kg DM extruded linseeds (LIN). For both breeds, replacing CPO with LIN had no effect (P > 0.05) on DM intake or milk yield, but reduced (P < 0.05) milk fat and protein yield (on average, from 760 to 706 and 573 to 552 g/day, respectively). Relative to CPO, the LIN treatment reduced (P < 0.01) total saturated fatty acid content and enhanced (P < 0.001) 18:3n-3 in milk, whereas breed by diet interactions were significant for milk fat 16:0, total trans fatty acid and conjugated linoleic acid concentrations. Increases in 18:3n-3 intake derived from LIN in the diet were transferred into milk with a mean marginal transfer efficiency of 1.8%. Proportionate changes in milk fatty acid composition were greater in the Jersey, highlighting the importance of diet–genotype interactions on mammary lipogenesis. More extensive studies are required to determine the role of genotype on milk fat composition responses to oilseeds in the diet.

Solid-state interconversions of coordination networks and hydrogen-bonded salts

Thermal or chemical treatment of crystalline 4,4-bipyridinium salts of [MCl4]2- (M=Co, Zn, Fe, or Pt) leads to HCl loss and formation of coordination network solids [{MCl2(4,4-bipy)}n]. For M=Co, Zn, and Fe, these solids can also be prepared by mechanochemical means. Their exposure to HCl vapor or the mechanochemical reaction of metal dichlorides with [4,4-H2bipy]Cl2 gives [4,4-H2bipy]2+ salts of [CoCl4]2-, [ZnCl4]2-, and, for the first time, [FeCl4]2-.

Alternative explanations for rising dissolved organic carbon export from organic soils

Since 1988, there has been, on average, a 91% increase in dissolved organic carbon (DOC) concentrations of UK lakes and streams in the Acid Waters Monitoring Network (AWMN). Similar DOC increases have been observed in surface waters across much of Europe and North America. Much of the debate about the causes of rising DOC has, as in other studies relating to the carbon cycle, focused on factors related to climate change. Data from our peat-core experiments support an influence of climate on DOC, notably an increase in production with temperature under aerobic, and to a lesser extent anaerobic, conditions. However, we argue that climatic factors may not be the dominant drivers of DOC change. DOC solubility is suppressed by high soil water acidity and ionic strength, both of which have decreased as a result of declining sulphur deposition since the 1980s, augmented during the 1990s in the United Kingdom by a cyclical decline in sea-salt deposition. Our observational and experimental data demonstrate a clear, inverse and quantitatively important link between DOC and sulphate concentrations in soil solution. Statistical analysis of 11 AWMN lakes suggests that rising temperature, declining sulphur deposition and changing sea-salt loading can account for the majority of the observed DOC trend. This combination of evidence points to the changing chemical composition of atmospheric deposition, particularly the substantial reduction in anthropogenic sulphur emissions during the last 20 years, as a key cause of rising DOC. The implications of rising DOC export for the carbon cycle will be very different if linked primarily to decreasing acid deposition, rather than to changes in climate, suggesting that these systems may be recovering rather than destabilising.

Export of dissolved organic carbon from an upland peatland during storm events: implications for flux estimates

Most of the dissolved organic carbon (DOC) exported from catchments is transported during storm events. Accurate assessments of DOC fluxes are essential to understand long-term trends in the transport of DOC from terrestrial to aquatic systems, and also the loss of carbon from peatlands to determine changes in the source/sink status of peatland carbon stores. However, many long-term monitoring programmes collect water samples at a frequency (e.g. weekly/monthly) less than the time period of a typical storm event (typically <1–2 days). As widespread observations in catchments dominated by organo-mineral soils have shown that both concentration and flux of DOC increases during storm events, lower frequency monitoring could result in substantial underestimation of DOC flux as the most dynamic periods of transport are missed. However, our intensive monitoring study in a UK upland peatland catchment showed a contrasting response to these previous studies. Our results showed that (i) DOC concentrations decreased during autumn storm events and showed a poor relationship with flow during other seasons; and that (ii) this decrease in concentrations during autumn storms caused DOC flux estimates based on weekly monitoring data to be over-estimated, rather than under-estimated, because of over rather than under estimation of the flow-weighted mean concentration used in flux calculations. However, as DOC flux is ultimately controlled by discharge volume, and therefore rainfall, and the magnitude of change in discharge was greater than the magnitude of decline in concentrations, DOC flux increased during individual storm events. The implications for long-term DOC trends are therefore contradictory, as increased rainfall could increase flux but cause an overall decrease in DOC concentrations from peatland streams. Care needs to be taken when interpreting long-term trends in DOC flux rather than concentration; as flux is calculated from discharge estimates, and discharge is controlled by rainfall, DOC flux and rainfall/discharge will always be well correlated.

Influence of drought-induced acidification on the mobility of dissolved organic carbon in peat soils

A strong relationship between dissolved organic carbon (DOC) and sulphate (SO42−) dynamics under drought conditions has been revealed from analysis of a 10-year time series (1993–2002). Soil solution from a blanket peat at 10 cm depth and stream water were collected at biweekly and weekly intervals, respectively, by the Environmental Change Network at Moor House-Upper Teesdale National Nature Reserve in the North Pennine uplands of Britain. DOC concentrations in soil solution and stream water were closely coupled, displaying a strong seasonal cycle with lowest concentrations in early spring and highest in late summer/early autumn. Soil solution DOC correlated strongly with seasonal variations in soil temperature at the same depth 4-weeks prior to sampling. Deviation from this relationship was seen, however, in years with significant water table drawdown (>−25 cm), such that DOC concentrations were up to 60% lower than expected. Periods of drought also resulted in the release of SO42−, because of the oxidation of inorganic/organic sulphur stored in the peat, which was accompanied by a decrease in pH and increase in ionic strength. As both pH and ionic strength are known to control the solubility of DOC, inclusion of a function to account for DOC suppression because of drought-induced acidification accounted for more of the variability of DOC in soil solution (R2=0.81) than temperature alone (R2=0.58). This statistical model of peat soil solution DOC at 10 cm depth was extended to reproduce 74% of the variation in stream DOC over this period. Analysis of annual budgets showed that the soil was the main source of SO42− during droughts, while atmospheric deposition was the main source in other years. Mass balance calculations also showed that most of the DOC originated from the peat. The DOC flux was also lower in the drought years of 1994 and 1995, reflecting low DOC concentrations in soil and stream water. The analysis presented in this paper suggests that lower concentrations of DOC in both soil and stream waters during drought years can be explained in terms of drought-induced acidification. As future climate change scenarios suggest an increase in the magnitude and frequency of drought events, these results imply potential for a related increase in DOC suppression by episodic acidification.

Have increased dissolved organic carbon (DOC) losses from UK peat and organo-mineral soils been driven by the decline in acid rain?

Dissolved organic carbon (DOC) concentrations have been rising in streams and lakes draining catchments with organic soils across Northern Europe. These increases have shown a correlation with decreased sulphate and chloride concentrations. One hypothesis to explain this phenomenon is that these relationships are due an increased in DOC release from soils to freshwaters, caused by a decline in pollutant sulphur and sea-salt deposition. We carried out controlled deposition experiments in the laboratory on intact peat and organomineral O-horizon cores to test this hypothesis. Preliminary data showed a clear correlation between the change in soil water pH and change in DOC concentrations, however uncertainty still remains about whether this is due to changes in biological activity or chemical solubility.

Molecular dynamics simulations of threadlike cetyltrimethylammonium chloride micelles: effects of sodium chloride and sodium salicylate salts

We use atomistic molecular dynamics simulations to probe the effects of added sodium chloride (NaCl) and sodium salicylate (NaSal) salts on the spherical-to-threadlike micelle shape transition in aqueous solutions of cetyltrimethylammonium chloride (CTAC) surfactants. Long threadlike micelles are found to be unstable and break into spherical micelles at low concentrations or NaCl, but remain stable for 20 ns above a threshold value of [NaCl] approximate to 3.0 M, which is about 2.5 times larger than the experimental salt concentration at which the transition between spherical and rodlike micelles occurs. The chloride counterions associate weakly oil the surface of the CTAC micelles with the degree of counterion dissociation decreasing slightly with increasing [NaCl] on spherical micelles, but dropping significantly on the threadlike micelles tit high [NaCl]. This effect indicates that the electrolyte ions drive the micellar shape transition by screening the electrostatic repulsions between the micellar headgroups, The aromatic salicylate counterions, on the other hand, penetrate inside the micelle with their hydrophilic groups staying in the surfactant headgroup region and the hydrophobic groups partially embedded into the hydrophobic core of the micelle. The strong association of the salicylate ions with the surfactant headgroups leads to dense packing of the surfactant molecules, which effectively reduces the surface area per surfactant, and increases intramicellar ordering of the surfactant headgroups, favoring the formation of long threadlike micelles. Simulation predictions of the geometric and electrostatic properties of the spherical and threadlike micelles are in good agreement with experiments.

Supramolecular assemblies of metal ions in complex bimetallic and trimetallic salts based on hexacyanoferrate(III) ion

Two complex heterometallic salts with formulae Tl-6[Fe(CN)(6)](1) (33)(NO3)(OH) (1) and [Co(bpy)(2)(CN)(2)](2){[Ag(CN)(2)](0) (5)[Fe(CN)(6)](0) (5)} 8H(2)O (2) have been synthesized and fully characterized Single crystal X-ray analyses reveal that compound 1 is comprised of discrete Tl+ cations and [Fe(CN)(6)](3-) anions together with OH- and NO3- anions Compound 2 contains [Co(bpy)(2)(CN)(2)](+) cations and {[Ag(CN)(2)][Fe(CN)(6)]}(-) anions together with eight molecules of water of crystallization Both structures form unprecedented three-dimensional supramolecular networks via non covalent interactions Another important observation is that the stereochemically active inert (lone) pair present on Tl+ plays little role in controlling the structure of 1 The water molecules in 2 play important roles in providing stability organizing a supramolecular network through hydrogen bonding In the syntheses of 1 and 2 Fe(II) is oxidized to Fe(III) and Co(II) to Co(III) respectively facilitating the formation of the salts that are obtained Both compounds exhibit photoluminescence emission in solution near the visible region.

Synthesis, X-ray crystal structures and properties of complex salts and sterically crowded heteroleptic complexes of group 10 metal ions with aromatic sulfonyl dithiocarbimates and triphenylphosphine ligand

Two new complex salts of the form (Bu4N)(2)[Ni(L)(2)] (1) and (Ph4P)(2)[Ni(L)(2)] (2) and four heteroleptic complexes cis-M(PPh3)(2)(L) [M = Ni(II) (3), Pd(II) (4), L = 4-CH3OC6H4SO2N=CS2] and cis-M(PPh3)(2)(L') [M = Pd(II) (5), Pt(II) (6), L' = C6H5SO2N=CS2] were prepared and characterized by elemental analyses, IR, H-1, C-13 and P-31 NMR and UV-Vis spectra, solution and solid phase conductivity measurements and X-ray crystallography. A minor product trans-Pd(PPh3)(2)(SH)(2), 4a was also obtained with the synthesis of 4. The NiS4 and MP2S2 core in the complex salts and heteroleptic complexes are in the distorted square-plane whereas in the trans complex, 4a the centrosymmetric PdS2P2 core is perforce square planar. X-ray crystallography revealed the proximity of the ortho phenyl proton of the PPh3 ligand to Pd(II) showing rare intramolecular C-H center dot center dot center dot Pd anagostic binding interactions in the palladium cis-5 and trans-4a complexes. The complex salts with sigma(rt) values similar to 10 (5) S cm (1) show semi-conductor behaviors. The palladium and platinum complexes show photoluminescence properties in solution at room temperature.