•Aquatic dissolved and particulate organic matter composition varied spatially.•Physical location, land use and vegetation cover affected organic matter composition.•Organic matter composition could ...be grouped into clusters with similar traits to maximise water treatment efficiency.
Water supply companies with reservoirs in peatland areas need to know how land use and vegetation cover in their supply catchments impact the amount and composition of aquatic organic matter in raw waters. Drinking water treatment processes remove organic matter from potable supplies, but recent increases in concentration and changes in composition have made this more difficult. This study analysed the composition of aquatic organic matter from peatland catchments in the UK and Faroe Islands. Both dissolved organic matter (DOM) and particulate organic matter (POM) compositions varied spatially, but these differences were not consistent as water moved through catchments, from headwaters and peatland pools to lake and reservoir outlets. These data showed that lakes and reservoirs are acting as flocculation hotspots, processing OM, releasing carbon (C), hydrogen (H) and oxygen (O) compounds to the atmosphere, and resulting in OM with higher N content. DOM compositions could be grouped into five clusters, showing that water treatment processes can be maximised to target ‘envelopes’ or clusters of DOM compositions. Catchment factors such as land use, vegetation cover, percentage peat cover and catchment area are good indicators of OM compositions likely to be present in a reservoir, and can guide water companies to maximise efficiency of their raw water treatment processes.
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Studies of dissolved organic matter (DOM) composition have used several different methods to concentrate and extract the DOM from fresh water, but the impact of these methods on the composition of ...the DOM is relatively unknown, as very few studies use more than one method to compare results. The aim of this study was to use several methods, frequently used in the scientific literature, to concentrate and extract DOM from fresh water and compare the elemental and functional group composition of the extracted DOM. In addition, the cost, in terms of money, resources and time, were assessed for each method. The results showed that the elemental and functional group composition of the extracted DOM varied between methods significantly. The methods that yielded the most similar and reproducible DOM results were rotary evaporation, dry-down at 60 °C and freeze-drying. Although each of these methods required a relatively expensive piece of laboratory equipment, this was a ‘one-off’ cost, and consumables and time per sample were relatively low. This study highlights the dangers of comparing DOM data from different studies when the DOM has been extracted via different methods. In future, it is recommended that studies of DOM composition report their methods of extraction clearly and consistently, ideally using one (or more) of the methods showing reliable results here.
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•Methods of extracting dissolved organic matter from freshwaters vary in efficiency.•Dissolved organic matter was extracted from freshwaters in the UK.•Several methods were evaluated, and the time, cost and results of each assessed.•Rotary evaporation, freeze-drying and dry-down gave the most consistent results.
Temozolomide (TMZ) is the standard first line treatment for malignant glioma, reaching "blockbuster" status in 2010, yet it remains the only drug in its class. The main constraints on the clinical ...effectiveness of TMZ therapy are its requirement for active DNA mismatch repair (MMR) proteins for activity, and inherent resistance through O6-methyl guanine-DNA methyl transferase (MGMT) activity. Moreover, acquired resistance, due to MMR mutation, results in aggressive TMZ-resistant tumour regrowth following good initial responses. Much of the attraction in TMZ as a drug lies in its PK/PD properties: it is acid stable and has 100% oral bioavailability; it also has excellent distribution properties, crosses the blood-brain barrier, and there is direct evidence of tumour localisation. This review seeks to unravel some of the mysteries of the imidazotetrazine class of compounds to which TMZ belongs. In addition to an overview of different synthetic strategies, we explore the somewhat unusual chemical reactivity of the imidazotetrazines, probing their mechanisms of reaction, examining which attributes are required for an active drug molecule and reviewing the use of this combined knowledge towards the development of new and improved anti-cancer agents.
Temozolomide (TMZ) a DNA alkylating agent, is the standard-of-care for brain tumors, such as glioblastoma multiforme (GBM). Although the physicochemical and pharmacokinetic properties of TMZ, such as ...chemical stability and the ability to cross the blood-brain barrier (BBB), have been questioned in the past, the acquired chemoresistance has been the main limiting factor of long-term clinical use of TMZ. In the present study, an L-type amino acid transporter 1 (LAT1)-utilizing prodrug of TMZ (TMZ-AA, 6) was prepared and studied for its cellular accumulation and cytotoxic properties in human squamous cell carcinoma, UT-SCC-28 and UT-SCC-42B cells, and TMZ-sensitive human glioma, U-87MG cells that expressed functional LAT1. TMZ-AA 6 accumulated more effectively than TMZ itself into those cancer cells that expressed LAT1 (UT-SCC-42B). However, this did not correlate with decreased viability of treated cells. Indeed, TMZ-AA 6, similarly to TMZ itself, required adjuvant inhibitor(s) of DNA-repair systems, O6-methylguanine-DNA methyl transferase (MGMT) and base excision repair (BER), as well as active DNA mismatch repair (MMR), for maximal growth inhibition. The present study shows that improving the delivery of this widely-used methylating agent is not the main barrier to improved chemotherapy, although utilizing a specific transporter overexpressed at the BBB or glioma cells can have targeting advantages. To obtain a more effective anticancer prodrug, the compound design focus should shift to altering the major DNA alkylation site or inhibiting DNA repair systems.
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•How will the oxidation state of northern ecosystems respond to future change?•Oxidative ratio (OR) is calculated for the first time along a latitudinal transect.•Results show an increase in OR with ...latitude from 1.03 to 1.09.•Findings suggest an increase in organic matter oxidation state under future change.
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The oxidative ratio (OR) of an ecosystem, which reflects the ratio of O2:CO2 associated with ecosystem gas exchanges, is an important parameter in understanding the sink of CO2 represented by the terrestrial biosphere. There is a growing body of ecosystem-based approaches to understand OR; however, there are still a number of unknowns. This study addressed two gaps in our understanding of the oxidation of the terrestrial biosphere: (1) What is the oxidation state of Arctic ecosystems, and in particular permafrost soils? (2) Will coupled climate and land use change cause the terrestrial organic matter oxidation state to change? The study considered eight locations along a transect from southern Sweden to northern Norway and sampled different organic matter types (soil, litter, trees, and herbaceous vegetation) as well as different soil orders (Inceptisols, Spodosols, Histosols, and Gelisols). The study showed that although there was no difference between soil orders, there was a significant effect due to location with OR increasing from 1.03 at the southernmost location to 1.09 in the northernmost location; this increase is independent of soil order or type of organic matter. The pattern of post hoc differences in the OR with latitude suggests that the increase in OR is correlated with the northern limit of arable agriculture. The study suggests that the combined effects of climate and land use change could lead to a decrease in terrestrial organic matter OR and an increase in its oxidation state.
Open‐water perennial pools are common natural features of peatlands globally, and peatland restoration often results in new pool creation, yet the concentrations of different forms of aquatic carbon ...(C) in natural and artificial restoration pools are not well studied. We compared carbon concentrations in both natural pools and restoration pools (4–15 years old) on three blanket peatlands in northern Scotland. At all sites, restoration pools were more acidic and had mean dissolved organic carbon (DOC) concentrations in restoration pools of 23, 22, and 31 mg L−1 compared with natural pool means of 11, 11 and 15 mg L−1 respectively across the three sites. Restoration pools had a greater fulvic acid prevalence than the natural pools and their DOC was more aromatic. Restoration pools were supersaturated with dissolved CO2 at around 10 times atmospheric levels, whereas for natural pools, CO2 concentrations were just above atmospheric levels. Dissolved CH4 concentrations were not different between pool types, but were ~200 times higher than atmospheric levels. Regular sampling at one of the peatland sites over 2.5 years showed that particulate organic carbon (POC) concentrations were generally below 7 mg L−1 except during the warm, dry summer of 2013. At this regularly‐sampled site, natural pools were found to process DOC so that mean pool outflow concentrations in overland flow were significantly lower than mean inflow DOC concentrations. Such an effect was not found for the restoration pools. Soil solution and pool water chemistry, and relationships between DOC and CO2 concentrations suggest that different processes are controlling the transformation of C, and therefore the form and amount of C, in natural pools compared to restoration pools.
Natural and artificial pool features at the three study locations
A practical and efficient entry to spirocyclic oxindoles from readily accessible anilide precursors, using only catalytic amounts of an inexpensive copper salt together with air as the sole ...re-oxidant, is described. In addition to providing access to a broad range of spiro-oxindole products, the utility of this method is demonstrated in a formal synthesis of the natural product, horsfiline.
Perennial pools are common natural features of peatlands, and their hydrological functioning and turnover may be important for carbon fluxes, aquatic ecology, and downstream water quality. Peatland ...restoration methods such as ditch blocking result in many new pools. However, little is known about the hydrological function of either pool type. We monitored six natural and six artificial pools on a Scottish blanket peatland. Pool water levels were more variable in all seasons in artificial pools having greater water level increases and faster recession responses to storms than natural pools. Pools overflowed by a median of 9 and 54 times pool volume per year for natural and artificial pools, respectively, but this varied widely because some large pools had small upslope catchments and vice versa. Mean peat water‐table depths were similar between natural and artificial pool sites but much more variable over time at the artificial pool site, possibly due to a lower bulk specific yield across this site. Pool levels and pool‐level fluctuations were not the same as those of local water tables in the adjacent peat. Pool‐level time series were much smoother, with more damped rainfall or recession responses than those for peat water tables. There were strong hydraulic gradients between the peat and pools, with absolute water tables often being 20–30 cm higher or lower than water levels in pools only 1–4 m away. However, as peat hydraulic conductivity was very low (median of 1.5 × 10−5 and 1.4 × 10−6 cm s−1 at 30 and 50 cm depths at the natural pool site), there was little deep subsurface flow interaction. We conclude that (a) for peat restoration projects, a larger total pool surface area is likely to result in smaller flood peaks downstream, at least during summer months, because peatland bulk specific yield will be greater; and (b) surface and near‐surface connectivity during storm events and topographic context, rather than pool size alone, must be taken into account in future peatland pool and stream chemistry studies.
Few studies have quantified the role of in-stream processes on net dissolved and particulate organic carbon (DOC and POC, respectively) export from peatland catchments, and those that have offer ...conflicting evidence. In this study, we evaluated evidence for active organic matter processing under field conditions, via a coordinated campaign across four UK catchments with peatland headwaters, targeted on potential ‘hotspots’ and ‘hot moments’ of physico-chemical carbon cycling. We hypothesised that specific hotspots and hot moments would occur where waters enriched with DOC and POC sourced from headwaters are exposed to: (1) mixing with freshwaters of different pH, conductivity and metal concentrations; and (2) mixing with seawater during autumn when DOC concentrations were at their highest. We observed instances of POC removal in headwaters, and potential for rapid conversion between dissolved and particulate carbon forms and for net removal of peat-derived carbon at confluences further downstream (where observed, on the order of 52–75 % for POC, and 5–44 % for DOC). Estuary transect surveys indicated that up to 30 % of fluvial DOC can be removed under high flow conditions. However, in the majority of cases concentrations remained within the range that would be expected based on conservative transport. These findings indicate that rapid (e.g. solubility-related) processes within the river system may be important but sporadic, thus are unlikely to provide major removal pathways for peat-derived organic carbon.
We consider how the stoichiometry and energy content of organic matter reservoirs and fluxes through and from a peatland enable the fluxes and storage of carbon within a peatland to be constrained. ...We include the elemental composition of the above‐ and below‐ground biomass, litter, the peat profile, and the dissolved and particulate organic matter within a blanket bog in northern England for which the C budget has previously been measured. The study shows, based only on the elemental composition, and calculation of oxidation and energy contents, that: (a) Dissolved organic carbon (DOC) in first‐order streams is significantly more oxidized than in peat pore water but that there was no significant difference in organic carbon oxidation state down the peat profile; (b) The occurrence and speciation of N uptake and release in the peatland with N used and recycled can be predicted; (c) The relatively high oxidation state of DOC in stream water acts as an endpoint for peat‐forming reactions; (d) Methanogenesis does not result in deep peat formation as its requirement for energy consumes too much organic matter to form residual peat at depth; (e) Sulfate reduction does occur during the formation of deep peat; (f) Organic matter elemental composition could be constrained to within three bounding equations though the proportions of carbon species could not be specified. (g) The formation of deep peat in this catchment could only be achieved if the dissolved organic matter (DOM) in the peat pore water is the dominant electron acceptor and energy source in the production of residual organic matter; however, it is unclear as to the flux of DOM up or down the peat profile.
Plain Language Summary
Peatlands are a vital terrestrial carbon store and so understanding their carbon budget has been a common measure of the health of those peatlands. Measuring carbon budgets a long and expensive process. However, we propose that the reactions of organic matter in peatlands must be constrained, like all chemical reactions, by stoichiometry and by enthalpy. Using elemental analysis of peat organic matter this study could reconstruct the C budget of a peatland and show which reactions are the most important.
Key Points
Study applies rules of stoichiometry and enthalpy balance to understand carbon budgets of peatlands
Methanogenesis does not result in deep peat formation as it requires too much energy to form residual organic matter at depth
Deep peat formation could only be achieved if the dissolved organic matter in the peat pore water was the dominant electron acceptor
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