Mid-infrared spectroscopy as a potential tool for reconstructing lake salinity

Many aquatic ecosystems in Australia are impacted or threatened by salinisation; however, there is a paucity of records detailing the changes in salinity of individual water bodies that extend beyond a few decades. One way to overcome this issue is the use of inference models, which have typically been based on biological proxies. This pilot project investigates the potential for mid-infrared spectroscopy (MIRS) to provide an alternative method of reconstructing past salinity levels in Australian lakes. A small (19 lakes) calibration dataset was used to develop a MIRS-based lake water salinity inference model (measured vs. inferred salinity, based on leave-one-out cross-validation, R2 = 0.64). This model and a previously published diatom–salinity model were both used to infer salinity levels in Tower Hill Lake in south-eastern Australia, over the last 60 years. Comparisons between these reconstructions and measured salinity data from Tower Hill Lake indicate that salinities inferred by the MIRS model more closely resembled the measured values than those produced using the diatom model, predominantly in terms of the actual values inferred, but also with regard to the trends observed. This supports the hypothesis that MIRS can provide a valuable new tool for reconstructing lake salinity.Laura Cunningham, John Tibby, Sean Forrester, Cameron Barr and Jan Skjemsta

Forest-derived lignin biomarkers in an Australian oxisol decrease substantially after 90 years of pasture

The dynamics of soil organic matter are a key factor in controlling the terrestrial carbon cycle. Compound specific stable carbon isotope analysis has given new insight in to the stability of individual organic molecules in soil. For lignin, one of the major plant compounds, available data suggest the existence of both a labile (turnover time <1 year) and a relatively stable (turnover time in the range of decades) pool. However, these data derive almost exclusively from agricultural soils in temperate climates. In order to extend the range both in ecosystem type and observed time span, we analysed a pasture soil in subtropical Australia that had experienced a land use change from rainforest 90 years earlier. We determined the concentration and isotopic signature of lignin biomarkers and compared them to those in an existing rainforest soil nearby and to samples of the respective vegetation. The land use change shifted both the relative abundance of lignin biomarkers and their isotopic signatures. In particular, the isotope data indicate that the pasture soil contains only small proportions of inherited rainforest-derived lignin biomarkers, which are mostly close to or below detection limit. These drastic changes in biomarker composition indicate that the original lignin structure had little chance to persist in this soil over a century. Thus, the stable soil organic carbon identified an earlier study of this soil is probably highly altered material and lignin biomarkers are not a suitable proxy of this stable carbon

Only small changes in soil organic carbon and charcoal concentrations found one year after experimental slash-and-burn in a temperate deciduous forest

International audienceAnthropogenic fires affected the temperate deciduous forests of Central Europe over millennia. Biomass burning releases carbon to the atmosphere and produces charcoal, which potentially contributes to the stable soil carbon pools and is an important archive of environmental history. The fate of charcoal in soils of temperate deciduous forests, i.e. the processes of charcoal incorporation and transportation, and the effects on soil organic matter are still not clear. In a long-term experimental burning site, we investigated the effects of slash-and-burn and determined soil organic carbon, charcoal carbon and nitrogen concentrations and the soil lightness of colour (L*) in the topmost soil material (0?1, 1?2.5 and 2.5?5 cm depths) before, immediately after the fire and one year after burning. The main results are that (i) only few charcoal particles from the forest floor were incorporated into the soil matrix by soil mixing animals. In 0?1 cm and during one year, the charcoal C concentrations increased only by 0.4 g kg?1 and the proportion of charcoal C to SOC concentrations increased from 2.8 to 3.4%; (ii) the SOC concentrations did not show any significant differences; (iii) soil lightness significantly decreased in the topmost soil layer and correlated with the concentrations of charcoal C (r=-0.87**) and SOC (r=?0.94**) in samples 0?5 cm. We concluded that the soil colour depends on the proportion of aromatic charcoal carbon in total organic matter and that Holocene burning could have influenced soil charcoal concentrations and soil colour

Influence of production variables and starting material on charcoal stable isotopic and molecular characteristics

We present a systematic study on the effect of starting species, gas composition, temperature, particle size and duration of heating upon the molecular and stable isotope composition of high density (mangrove) and low density (pine) wood. In both pine and mangrove, charcoal was depleted in o13C relative to the starting wood by up to 1.6&#37; and 0.8&#37;, respectively. This is attributed predominantly to the progressive loss of isotopically heavier polysaccharides, and kinetic effects of aromatization during heating. However, the pattern of o13C change was dependant upon both starting species and atmosphere, with different structural changes associated with charcoal production from each wood type elucidated by Solid-State o13C Nuclear Magnetic Resonance Spectroscopy. These are particularly evident at lower temperatures, where variation in the oxygen content of the production atmosphere results in differences in the thermal degradation of cellulose and lignin. It is concluded that production of charcoal from separate species in identical conditions, or from a single sample exposed to different production variables, can result in significantly different o13C of the resulting material, relative to the initial wood. These results have implications for the use of charcoal isotope composition to infer past environmental change

Australian climate-carbon cycle feedback reduced by soil black carbon

Annual emissions of carbon dioxide from soil organic carbon are an order of magnitude greater than all anthropogenic carbon dioxide emissions taken together1. Global warming is likely to increase the decomposition of soil organic carbon, and thus the release of carbon dioxide from soils2,3,4,5, creating a positive feedback6,7,8,9. Current models of global climate change that recognize this soil carbon feedback are inaccurate if a larger fraction of soil organic carbon than postulated has a very slow decomposition rate. Here we show that by including realistic stocks of black carbon in prediction models, carbon dioxide emissions are reduced by 18.3 and 24.4% in two Australian savannah regions in response to a warming of 3 ∘C over 100 years1. This reduction in temperature sensitivity, and thus the magnitude of the positive feedback, results from the long mean residence time of black carbon, which we estimate to be approximately 1,300 and 2,600 years, respectively. The inclusion of black carbon in climate models is likely to require spatially explicit information about its distribution, given that the black carbon content of soils ranged from 0 to 82% of soil organic carbon in a continental-scale analysis of Australia. We conclude that accurate information about the distribution of black carbon in soils is important for projections of future climate change

Soil organic

[1] We quantified the effects of repeated, seasonal fires on soil organic carbon (SOC), black carbon (BC), and total N in controls and four fire treatments differing in frequency and season of occurrence in a temperate savanna. The SOC at 0-20 cm depth increased from 2044 g C m À2 in controls to 2393-2534 g C m À2 in the three treatments that included summer fire. Similarly, soil total N (0-20 cm) increased from 224 g N m À2 in the control to 251-255 g N m À2 in the treatments that included summer fire. However, winter fires had no effect on SOC or total N. Plant species composition coupled with lower d 13 C of SOC suggested that increased soil C in summer fire treatments was related to shifts in community composition toward greater relative productivity by C 3 species. Lower d 15 N of soil total N in summer fire treatments was consistent with a scenario in which N inputs &gt; N losses. The BC storage was not altered by fire, and comprised 13-17% of SOC in all treatments. Results indicated that fire and its season of occurrence can significantly alter ecosystem processes and the storage of C and N in savanna ecosystems

Assessment of hydropyrolysis as a method for the quantification of black carbon using standard reference materials

A wide selection of thermal, chemical and optical methods have been proposed for the quantification of black carbon (BC) in environmental matrices, and the results to date differ markedly depending upon the method used. A new approach is hydropyrolysis (hypy), where pyrolysis assisted by high hydrogen pressures (150 bar) facilitates the complete reductive removal of labile organic matter, so isolating a highly stable portion of the BC continuum (defined as BChypy). Here, the potential of hypy for the isolation and quantification of BC is evaluated using the 12 reference materials from the International BC Ring Trial, comprising BC-rich samples, BC-containing environmental matrices and BC-free potentially interfering materials. By varying the hypy operating conditions, it is demonstrated that lignocellulosic, humic and other labile organic carbon material (defined as non-BChypy) is fully removed by 550 °C, with hydrogasification of the remaining BChypy not commencing until over 575 °C. The resulting plateau in sample mass and carbon loss is apparent in all of the environmental samples, facilitating BC quantification in a wide range of materials. The BChypy contents for all 12 ring trial samples fall within the range reported in the BC inter-comparison study, and systematic differences with other methods are rationalised. All methods for BC isolation, including hypy are limited by the fact that BC cannot be distinguished from extremely thermally mature organic matter; for example in high rank coals. However, the data reported here indicates that BChypy has an atomic H/C ratio of less than 0.5 and therefore comprises a chemically well-defined polyaromatic structure in terms of the average size of peri-condensed aromatic clusters of &gt;7 rings (24 carbon atoms), that is consistent across different sample matrices. This, together with the sound underlying rationale for the reductive removal of labile organic matter, makes hypy an ideal approach for matrix independent BC quantification. The hypy results are extremely reproducible, with BChypy determinations from triplicate analyses typically within ±2% across all samples, limited mainly by the precision of the elemental analyser

Pyrogenic Carbon Contributes Substantially to Carbon Storage in Intact and Degraded Northern Peatlands

Pyrogenic carbon (PyC) derives from incomplete combustion of organic matter and is ubiquitous in terrestrial and aquatic systems. Most PyC is inherently more stable against decomposition than plant residues, and PyC therefore forms an important component of the global carbon (C) cycle. During the Holocene, about 436 Pg organic C accumulated in northern peatlands, and we hypothesize that PyC may contribute substantially to that C stock. We studied 70 samples from 19 intact and degraded European peatland sites and analyzed their PyC content by 13C nuclear magnetic resonance spectroscopy and molecular modeling and peat age and accumulation by radiocarbon dating. Classification of a peatland as either intact or degraded was based on the comparison between apparent and expected long-term C accumulation rates. On average, PyC amounted for 13·5% of soil C across sites, and accounted for up to 50% at single sites. The amount of PyC increased significantly with peat age. Degraded peatlands had lost approximately 56 kg C m−2, half of their former C stock. However, degraded peat had higher PyC contents than intact one. Selective enrichment of PyC during both peat build-up and decomposition seems to be an important factor fostering PyC accumulation. Assignment of our results to peatlands of the northern hemisphere, stratified by age, revealed an estimated PyC stock of 62 (±22) Pg. Our estimate indicates a substantial and hitherto unquantified contribution of northern peatlands to global PyC storage

Release of Nitrogen and Phosphorus from Poultry Litter Amended with Acidified Biochar

Application of poultry litter (PL) to soil may lead to nitrogen (N) losses through ammonia (NH3) volatilization and to potential contamination of surface runoff with PL-derived phosphorus (P). Amending litter with acidified biochar may minimize these problems by decreasing litter pH and by retaining litter-derived P, respectively. This study evaluated the effect of acidified biochars from pine chips (PC) and peanut hulls (PH) on NH3 losses and inorganic N and P released from surface-applied or incorporated PL. Poultry litter with or without acidified biochars was surface-applied or incorporated into the soil and incubated for 21 d. Volatilized NH3 was determined by trapping it in acid. Inorganic N and P were determined by leaching the soil with 0.01 M of CaCl2 during the study and by extracting it with 1 M KCl after incubation. Acidified biochars reduced NH3 losses by 58 to 63% with surface-applied PL, and by 56 to 60% with incorporated PL. Except for PH biochar, which caused a small increase in leached NH4 +-N with incorporated PL, acidified biochars had no effect on leached or KCl-extractable inorganic N and P from surface-applied or incorporated PL. These results suggest that acidified biochars may decrease NH3 losses from PL but may not reduce the potential for P loss in surface runoff from soils receiving PL