Source and age of dissolved and gaseous carbon in a peatland–riparian–stream continuum: a dual isotope (14C and δ13C) analysis

Radiocarbon isotopes are increasingly being used to investigate the age and source of carbon released from peatlands. Here we use combined ¹⁴C and δ¹³C measurements to determine the isotopic composition of soil and soil decomposition products [dissolved organic carbon (DOC), CO₂ and CH₄] in a peatland–riparian–stream transect, to establish the isotopic signature and potential connectivity between carbon pools. Sampling was conducted during two time periods in 2012 to investigate processes under different temperature, hydrological and flux conditions. Isotopic differences existed in the peatland and riparian zone soil organic matter as a result of the riparian depositional formation. The peatland had a mean radiocarbon age of 551 ± 133 years BP, with age increasing with depth, and δ¹³C values consistent with C3 plant material as the primary source. In contrast the riparian zone had a much older radiocarbon age of 1,055 ± 107 years BP and showed no age/depth relationship; δ¹³C in the riparian zone was also consistent with C3 plant material. With the exception of DOC in September, soil decomposition products were predominately >100 %modern with ¹⁴C values consistent with derivation from organic matter fixed in the previous 5 years. Emissions of CO₂ and CH₄ from the soil surface were also modern. In contrast, CO₂ and CH₄ evaded from the stream surface was older (CH₄: 310–537 years BP, CO₂: 36 years BP to modern) and contained a more complex mix of sources combining soil organic matter and geogenic carbon. The results suggest considerable vertical transport of modern carbon to depth within the soil profile. The importance of modern recently fixed carbon and the differences between riparian and stream isotopic signatures suggests that the peatland (not the riparian zone) is the most important source of carbon to stream water.     

Thermoregulatory plasticity in free-ranging vervet monkeys,Chlorocebus pygerythrus

We used implanted miniature data loggers to obtain the first measurements of body temperature from a free-ranging anthropoid primate. Vervet monkeys (Chlorocebus pygerythrus) living in a highly seasonal, semi-arid environment maintained a lower mean 24-h body temperature in winter (34.6 ± 0.5 °C) than in summer (36.2 ± 0.1 °C), and demonstrated increased heterothermy (as indexed by the 24-h amplitude of their body temperature rhythm) in response to proximal environmental stressors. The mean 24-h amplitude of the body temperature rhythm in summer (2.5 ± 0.1 °C) was lower than that in winter (3.2 ± 0.4 °C), with the highest amplitude for an individual monkey (5.6 °C) recorded in winter. The higher amplitude of the body temperature rhythm in winter was a consequence primarily of lower 24-h minimum body temperatures during the nocturnal phase, when monkeys were inactive. These low minimum body temperatures were associated with low black globe temperature (GLMM, β = 0.046, P < 0.001), short photoperiod (β = 0.010, P < 0.001) and low rainfall over the previous 2 months, which we used as a proxy for food availability (β = 0.001, P < 0.001). Despite the lower average winter minimum body temperatures, there was no change in the lower modal body temperature between winter and summer. Therefore, unlike the regulated physiological adjustments proposed for torpor or hibernation, these minimum winter body temperatures did not appear to reflect a regulated reduction in body temperature. The thermoregulatory plasticity nevertheless may have fitness benefits for vervet monkeys.     

Photochemical degradation of citrate buffers leads to covalent acetonation of recombinant protein therapeutics

Novel acetone and aldimine covalent adducts were identified on the N‐termini and lysine side chains of recombinant monoclonal antibodies. Photochemical degradation of citrate buffers, in the presence of trace levels of iron, is demonstrated as the source of these modifications. The link between degradation of citrate and the observed protein modifications was conclusively established by tracking the citrate decomposition products and protein adducts resulting from photochemical degradation of isotope labeled ¹³C citrate by mass spectrometry. The structure of the acetone modification was determined by nuclear magnetic resonance (NMR) spectroscopy on modified–free glycine and found to correspond to acetone linked to the N‐terminus of the amino acid through a methyl carbon. Results from mass spectrometric fragmentation of glycine modified with an acetone adduct derived from ¹³C labeled citrate indicated that the three central carbons of citrate are incorporated onto protein amines in the presence of iron and light. While citrate is known to stoichiometrically decompose to acetone and CO₂ through various intermediates in photochemical systems, it has never been shown to be a causative agent in protein carbonylation. Our results point to a previously unknown source for the generation of reactive carbonyl species. This work also highlights the potential deleterious impact of trace metals on recombinant protein therapeutics formulated in citrate buffers.     

Dry deposition of ammonia gas drives species change faster than wet deposition of ammonium ions: evidence from a long‐term field manipulation

Although the effects of atmospheric nitrogen deposition on species composition are relatively well known, the roles of the different forms of nitrogen, in particular gaseous ammonia (NH₃), have not been tested in the field. Since 2002, we have manipulated the form of N deposition to an ombrotrophic bog, Whim, on deep peat in southern Scotland, with low ambient N (wet + dry = 8 kg N ha^?1 yr^?1) and S (4 kg S ha^?1 yr^?1) deposition. A gradient of ammonia (NH₃, dry N), from 70 kg N ha^?1 yr^?1 down to background, 3–4 kg N ha^?1 yr^?1 was generated by free air release. Wet ammonium (NH₄⁺, wet N) was provided to replicate plots in a fine rainwater spray (NH₄Cl at +8, +24, +56 kg N ha^?1 yr^?1). Automated treatments are coupled to meteorological conditions, in a globally unique, field experiment. Ammonia concentrations were converted to NH₃‐N deposition (kg N ha^?1) using a site/vegetation specific parameterization. Within 3 years, exposure to relatively modest deposition of NH₃, 20–56 kg NH₃‐N ha^?1 yr^?1 led to dramatic reductions in species cover, with almost total loss of Calluna vulgaris, Sphagnum capillifolium and Cladonia portentosa. These effects appear to result from direct foliar uptake and interaction with abiotic and biotic stresses, rather than via effects on the soil. Additional wet N by contrast, significantly increased Calluna cover after 5 years at the 56 kg N dose, but reduced cover of Sphagnum and Cladonia. Cover reductions caused by wet N were significantly different from and much smaller than those caused by equivalent dry N doses. The effects of gaseous NH₃ described here, highlight the potential for ammonia to destroy acid heathland and peat bog ecosystems. Separating the effects of gaseous ammonia and wet ammonium deposition, for a peat bog, has significant implications for regulatory bodies and conservation agencies.