Assessment of potential climate change impacts on peatland dissolved organic carbon release and drinking water treatment from laboratory experiments

Catchments draining peat soils provide the majority of drinking water in the UK. Over the past decades, concentrations of dissolved organic carbon (DOC) have increased in surface waters. Residual DOC can cause harmful carcinogenic disinfection by-products to form during water treatment processes. Increased frequency and severity of droughts combined with and increased temperatures expected as the climate changes, have potentials to change water quality. We used a novel approach to investigate links between climate change, DOC release and subsequent effects on drinking water treatment. We designed a climate manipulation experiment to simulate projected climate changes and monitored releases from peat soil and litter, then simulated coagulation used in water treatment. We showed that the ‘drought’ simulation was the dominant factor altering DOC release and affected the ability to remove DOC. Our results imply that future short-term drought events could have a greater impact than increased temperature on DOC treatability.

Simulated climate change impact on summer dissolved organic carbon release from peat and surface vegetation: implications for drinking water treatment

Uncertainty regarding changes in dissolved organic carbon (DOC) quantity and quality has created interest in managing peatlands for their ecosystem services such as drinking water provision. The evidence base for such interventions is, however, sometimes contradictory. We performed a laboratory climate manipulation using a factorial design on two dominant peatland vegetation types (Calluna vulgaris and Sphagnum Spp.) and a peat soil collected from a drinking water catchment in Exmoor National Park, UK. Temperature and rainfall were set to represent baseline and future conditions under the UKCP09 2080s high emissions scenario for July and August. DOC leachate then underwent standard water treatment of coagulation/flocculation before chlorination. C. vulgaris leached more DOC than Sphagnum Spp. (7.17 versus 3.00 mg g−1) with higher specific ultraviolet (SUVA) values and a greater sensitivity to climate, leaching more DOC under simulated future conditions. The peat soil leached less DOC (0.37 mg g−1) than the vegetation and was less sensitive to climate. Differences in coagulation removal efficiency between the DOC sources appears to be driven by relative solubilisation of protein-like DOC, observed through the fluorescence peak C/T. Post-coagulation only differences between vegetation types were detected for the regulated disinfection by-products (DBPs), suggesting climate change influence at this scale can be removed via coagulation. Our results suggest current biodiversity restoration programmes to encourage Sphagnum Spp. will result in lower DOC concentrations and SUVA values, particularly with warmer and drier summers.

Results from the Covered Catchment Experiment at Gårdsjön, Sweden, after ten years of clean precipitation treatment

The Covered Catchment Experiment at Gordsjon is a large scale forest ecosystem manipulation, where acid precipitation was intercepted by a 7000 m(2) plastic roof and replaced by 'clean precipitation' sprinkled below the roof for ten years between 1991 and 2001. The treatment resulted in a strong positive response of runoff quality. The runoff sulphate, inorganic aluminium and base cations decreased, while there was a strong increase in runoff ANC and a moderate increase in pH. The runoff continued to improve over the whole duration of the experiment. The achieved quality was, however, after ten years still considerably worse than estimated pre-industrial runoff at the site. Stable isotopes of sulphur were analysed to study the soil sulphur cycling. At the initial years of the experiment, the desorption of SO4 from the mineral soil appeared to control the runoff SO4 concentration. However, as the experiment proceeded, there was growing evidence that net mineralisation of soil organic sulphur in the humus layer was an additional source of SO4 in runoff. This might provide a challenge to current acidification models. The experiment convincingly demonstrated on a catchment scale, that reduction in acid deposition causes an immediate improvement of surface water quality even at heavily acidified sites. The improvement of the runoff appeared to be largely a result of cation exchange processes in the soil due to decreasing concentrations of the soil solution, while any potential change in soil base saturation seemed to be less important for the runoff chemistry over the short time period of one decade. These findings should be considered when interpreting and extrapolating regional trends in surface water chemistry to the terrestrial parts of ecosystems.

Synthesis and evaluation of novel boron-containing complexes of potential use for the selective treatment of malignant melanoma

Boron-containing complexes that have the potential to irreversibly accumulate in melanoma cells have been prepared by reaction of amino acids with 9-methoxy-9-borabicyclo[3.3.1]nonane. The ability of each complex to act as a substrate for tyrosinase has been probed by oximetry. Increased uptake of the lead candidate in a tyrosinase-rich cell line, compared with a tyrosinase-absent cell line, is reported, with results correlating well with that for a drug currently approved for BNCT.

Effects of cultural system (organic and conventional) on growth, photosynthesis and yield components of sweet corn (zea mays L.) under semi-arid environment

Organic sweet maize consists of a new industrial crop product. Field experiment was conducted to determine the effects of cultural systems on growth, photosynthesis and yield components of sweet maize crop (Zea mays L. F-1 hybrid 'Midas'). A randomized complete block design was employed with four replicates per treatment (organic fertilization: cow manure (5, 10 and 20 t ha(-1)), poultry manure (5, 10 and 20 t ha(-1)) and barley mulch (5, 10 and 20 t ha(-1)), synthetic fertilizer (240 kg N ha(-1)): 21-0-0 and control). The lowest dry weight, height and leaf area index and sod organic matter were measured in the control treatment. Organic matter content was proportionate to the amount of manure applied. The control plots had the lowest yield (1593 kg ha(-1)) and the double rate cow manure plots the had,greatest one. (6104 kg ha(-1)). High correlation between sweet corn yield and organic matter was registered. Moreover, the lowest values of 1000-grain weight were obtained with control plot. The fertilizer plot gave values which were similar to the full rate cow manure treatment. The photosynthetic race of the untreated control was significantly lower than that of the other treatments. The phorosynthetic rate increased as poultry manure and barley mulch ram decreased and as cow manure increased. Furthermore the untreated control had the lowest stomatal conductance and chlorophyll content. Our results indicated that sweet corn growth and yield in the organic plots was significantly higher than those in the conventional plots.

Novel solid networks containing Sn-H as a greener replacement for soluble alkyl Sn-H reagents in radical assisted organic synthesis

DiGrignard reagents of the form XMg(CH2)(n)MgX, where X = Br or I and n = 6, 8, 10 or 12, were allowed to react with PhSnCl3 to produce highly cross-linked Ph-Sn polymeric networks. The Sn-H moiety was incorporated into these insoluble network polymers by treatment with Br-2 and NaBH4. Excellent accessibility of the Sn-H was displayed by these solvent penetrable but insoluble networks, giving them higher Sn-H loadings than all previously reported supported reagents. These reagents were totally regenerable in NaBH4 for radical assisted organic synthesis and no detectable leaching of the Sn into solution was observed during these reactions.

Effects of ammonia treatment and undegradable protein supplementation on nutrient digestion of sheep fed on wheat straw based diets.

A study was conducted to investigate the effects of wheat straw ammonisation and supplementation with a rumen undegradable protein (UDP) source on nutrient digestion and nitrogen balance by lambs while diets were supplemented with kibbled carob pods as energy source. Ammonisation increased the crude protein content of wheat straw by nearly 100% and decreased the contents of neutral detergent fibre and acid detergent fibre by 7% and 1.7% respectively. Treating the straw with ammonia resulted in significant (P<0.01) increase in nitrogen (N) intake and intakes of organic matter (OM) and dry matter (DM) tended toward significance (P<0.1). The UDP source had no effect (P>0.05) on DM and OM intakes but resulted in an increase (P<0.05) of N intakes. Both, ammonization and UDP supplementation increased (P<0.01) the DM, OM and N digestibility. In conclusion, the results of this study suggest that ammonisation and UDP supplementation is a practical dietary manipulation option to improve the nutritional status of ruminants fed on roughage-based diets.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles representative of atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant time scales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semisolid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KMSUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

The effects of organic and conventional fertilizers on cereal aphids and their natural enemies

Aphids are important pests of spring cereals and their abundance and the impact of their natural enemies may be influenced by fertilizer regime.2We conducted a 2-year field study investigating the effects of organic slow-release and conventional fertilizers on cereal aphids, hymenopteran parasitoids and syrphid predators and considered how the effects of fertilizers on barley morphology and colour might influence these species.3Barley yield was greater in conventionally fertilized pots. Barley morphology was also affected by treatment: vegetative growth was greater under conventional treatments. Barley receiving organic fertilizers or no fertilizer was visually more attractive to aphids compared with plants receiving conventional fertilizers.4Aphids were more abundant in conventionally fertilized barley but the reason for this increased abundance was species specific. Metopolophium dirhodum was responding to fertilizer effects on plant morphology, whereas Rhopalosiphum padi was sensitive to the temporal availability of nutrients.5Syrphid eggs were more numerous in conventionally fertilized pots, whereas the response of parasitoids appeared to be dependent on the abundance of aphids, although the number of parasitoid mummies was low in both years.6This research shows that the fertilizer treatment used can affect numerous characteristics of plant growth and colour, which can then influence higher trophic levels. This knowledge might be used to make more informed fertilizer application choices.

Tritrophic effects of organic and conventional fertilisers on a cereal-aphid-parasitoid system

The impact of parasitoids on pests varies between conventional and low-intensity agricultural systems. Although the impacts on parasitoid natural enemies of many practices within these agricultural systems are well understood, the role of fertilisers has been less well studied. The effects of organic-based and conventional fertilisers on Hordeum vulgare L. (Poaceae), the aphid Metopolophium dirhodum Walker (Hemiptera: Aphididae), and its parasitoid Aphidius ervi Haliday (Hymenoptera: Braconidae) was investigated using cage release experiments and measures of aphid and parasitoid fitness were taken. Barley tiller number and aphid weight were increased by fertilisers, particularly under conventional treatments. Adult parasitoid size correlated positively with that of the host, M. dirhodum, whereas percentage parasitism was not affected by fertiliser treatment or host size. The results suggest that the increased parasitoid impact observed in some low-intensity or organic systems is not a direct result of fertiliser treatment. Our results indicate that fertiliser treatments that improve cereal-aphid fitness will improve parasitoid fitness as measured by parasitoid size but may not influence percentage parasitism.

Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separation in nuclear waste treatment: the effect of alkyl substitution on extraction properties and implications for ligand design

Four new 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligands, which contain either additional alkyl groups on the pyridine rings or seven-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of the additional alkyl substitution in the 4- and 4′-positions of the pyridine rings on their extraction properties with LnIII and AnIII cations in simulated nuclear waste solutions have been studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1H NMR spectroscopic titrations and ESI-MS. Although 13 formed both 1:1 and 1:2 complexes with LaIII and YIII, only 1:2 complexes were observed with EuIII and CeIII. Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the unsubstituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, alkyl-substitution was found to decrease the rates of metal-ion extraction of the ligands in both 1-octanol and cyclohexanone. A highly efficient (DAm > 10) and selective (SFAm/Eu > 90) extraction was observed for 12 and 13 in cyclohexanone and for 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed.

Acidity controls on dissolved organic carbon mobility in organic soils

Dissolved organic carbon (DOC) concentrations in surface waters have increased across much of Europe and North America, with implications for the terrestrial carbon balance, aquatic ecosystem functioning, water treatment costs and human health. Over the past decade, many hypotheses have been put forward to explain this phenomenon, from changing climate and land-management to eutrophication and acid deposition. Resolution of this debate has been hindered by a reliance on correlative analyses of time-series data, and a lack of robust experimental testing of proposed mechanisms. In a four-year, four-site replicated field experiment involving both acidifying and de-acidifying treatments, we tested the hypothesis that DOC leaching was previously suppressed by high levels of soil acidity in peat and organo-mineral soils, and therefore that observed DOC increases a consequence of decreasing soil acidity. We observed a consistent, positive relationship between DOC and acidity change at all sites. Responses were described by similar hyperbolic relationships between standardised changes in DOC and hydrogen ion concentrations at all sites, suggesting potentially general applicability. These relationships explained a substantial proportion of observed changes in peak DOC concentrations in nearby monitoring streams, and application to a UK-wide upland soil pH dataset suggests that recovery from acidification alone could have led to soil solution DOC increases in the range 46-126% by habitat type since 1978. Our findings raise the possibility that changing soil acidity may have wider impacts on ecosystem carbon balances. Decreasing sulphur deposition may be accelerating terrestrial carbon loss, and returning surface waters to a natural, high-DOC condition.

Peroxidative bromination and oxygenation of organic compounds: synthesis, X-ray crystal structure and catalytic implications of mononuclear and binuclear oxovanadium(V) complexes containing Schiffbase ligands

Treatment of of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H(2)L(1)) in methanol with aqueous NH(4)VO(3) solution in perchloric acid medium affords the mononuclear oxovanadium(V) complex [VOL(1)(MeOH)]-ClO(4) (1) as deep blue solid while the treatment of same solution of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H(2)L(1)) with aqueous solution of VOSO(4) leads to the formation of di-(mu-oxo) bridged vanadium(V) complex [VO(2)L(2)](2) (2) as green solid where HL(2) = (R,R)-N-salicylidene cyclohexane 1,2-diamine. The ligand HL(2) is generated in situ by the hydrolysis of one of the imine bonds of HL(1) ligand during the course of formation of complex [VO(2)L(2)](2) (2). Both the compounds have been characterized by single crystal X-ray diffraction as well as spectroscopic methods. Compounds 1 and 2 are to act as catalyst for the catalytic bromide oxidation and C-H bond oxidation in presence of hydrogen peroxide. The representative substrates 2,4-dimethoxy benzoic acid and para-hydroxy benzoic acids are brominated in presence of H(2)O(2) and KBr in acid medium using the above compounds as catalyst. The complexes are also used as catalyst for C-H bond activation of the representative hydrocarbons toluene, ethylbenzene and cyclohexane where hydrogen peroxide acts as terminal oxidant. The yield percentage and turnover number are also quite good for the above catalytic reaction. The oxidized products of hydrocarbons have been characterized by GC Analysis while the brominated products have been characterized by (1)H NMR spectroscopic studies.

The impact of climate change on the treatability of dissolved organic matter (DOM) in upland water supplies: A UK perspective

Climate change in the UK is expected to cause increases in temperatures, altered precipitation patterns and more frequent and extreme weather events. In this review we discuss climate effects on dissolved organic matter (DOM), how altered DOM and water physico-chemical properties will affect treatment processes and assess the utility of techniques used to remove DOM and monitor water quality. A critical analysis of the literature has been undertaken with a focus on catchment drivers of DOM character, removal of DOM via coagulation and the formation of disinfectant by-products (DBPs). We suggest that: (1) upland catchments recovering from acidification will continue to produce more DOM with a greater hydrophobic fraction as solubility controls decrease; (2) greater seasonality in DOM export is likely in future due to altered precipitation patterns; (3) changes in species diversity and water properties could encourage algal blooms; and (4) that land management and vegetative changes may have significant effects on DOM export and treatability but require further research. Increases in DBPs may occur where catchments have high influence from peatlands or where algal blooms become an issue. To increase resilience to variable DOM quantity and character we suggest that one or more of the following steps are undertaken at the treatment works: a) ‘enhanced coagulation’ optimised for DOM removal; b) switching from aluminium to ferric coagulants and/or incorporating coagulant aids; c) use of magnetic ion-exchange (MIEX) pre-coagulation; and d) activated carbon filtration post-coagulation. Fluorescence and UV absorbance techniques are highlighted as potential methods for low-cost, rapid on-line process optimisation to improve DOM removal and minimise DBPs.