Robert Van Hale

Experimental evidence for sequestering C with biochar by avoidance of CO2 emissions from original feedstock and protection of native soil organic matter

There is a need for further studies to compare the decomposition of biochar to that of the original feedstock and determine how these amendments affect the cycling of native organic matter (NOM) of different soils to improve our understanding of the resulting net C sequestration potential. A 510‐days incubation experiment was conducted (i) to investigate the evolution of CO2 from soils amended with either fresh corn stover (CS) or with biochars produced from fresh CS at either 350 (CS‐350) or 550 °C (CS‐550), and (ii) to evaluate the priming effect of these amendments on NOM decomposition. Two soil types were studied: an Alfisol and an Andisol, with organic C contents of 4% and 10%, respectively. Except for the controls (with no C addition), all treatments received 7.18 t C ha−1. We measured C efflux in short‐term intervals and its isotopic signature to distinguish between C evolved from C4 amendments and C3‐dominated NOM. Emission rates were then integrated for the whole time period to cover total emissions. Total CO2‐C evolved from the original C in fresh CS, CS‐350 and CS‐550 was greater in the Andisol (78%, 13% and 14%) than in the Alfisol (66%, 8% and 7%). For both soils, (i) no significant differences (P > 0.05) were observed in the rate of CO2 evolution between controls and biochar treatments; and (ii) total accumulated CO2 evolved from the uncharred amendment was significantly higher (P < 0.05) than that from the other treatments. In the Alfisol, a significant (P < 0.05) net positive priming effect on NOM decomposition was observed when amended with fresh CS, while the opposite was detected in biochar treatments. In the Andisol, no significant (P > 0.05) net priming effect was observed. A C balance indicated that the C lost from both biochar production and decomposition ‘broke even’ with that lost from fresh residue decomposition after <35 weeks. The ‘break‐even’ point was reached earlier in the Andisol, in which the fresh CS mineralizes faster. These results provided experimental evidence for the potential of biochar to sequester C and avoid CO2 emissions from original feedstock while protecting native soil organic matter.

Correlation of geographical location with stable isotope values of hydrogen and carbon of fatty acids from New Zealand milk and bulk milk powder.

The aim of this study was to investigate the correlation of δ²H and δ¹³C of bulk milk powder and milk powder fatty acids to their production region. A total of 46 milk powder samples from across New Zealand were collected and analyzed. Principal component analysis (PCA) showed that the δ²H and δ¹³C of four fatty acids (C4:0, C14:0, C16:0, C18:1) and bulk milk powder were found to be correlated with regional production area. Linear discriminant analysis (LDA) models were prepared using different combinations of bulk and fatty acid δ²H and δ¹³C. All models were effective in discriminating samples from the North and South Islands. The LDA model using just fatty acid δ²H and δ¹³C provided the best separation. Therefore, the isotopic composition of the aforementioned fatty acids can be utilized as a good biomarker in milk powder that conveys reliable isotopic information to track milk powders to their regional origin.

Isotopes and Trace Elements as Natal Origin Markers of Helicoverpa armigera – An Experimental Model for Biosecurity Pests

Protecting a nations primary production sector and natural estate is heavily dependent on the ability to determine the risk presented by incursions of exotic insect species. Identifying the geographic origin of such biosecurity breaches can be crucial in determining this risk and directing the appropriate operational responses and eradication campaigns, as well as ascertaining incursion pathways. Reading natural abundance biogeochemical markers using mass spectrometry is a powerful tool for tracing ecological pathways as well as provenance determination of commercial products and items of forensic interest. However, application of these methods to trace insects has been underutilised to date and our understanding in this field is still in a phase of basic development. In addition, biogeochemical markers have never been considered in the atypical situation of a biosecurity incursion, where sample sizes are often small, and of unknown geographic origin and plant host. These constraints effectively confound the interpretation of the one or two isotope geo-location markers systems that are currently used, which are therefore unlikely to achieve the level of provenance resolution required in biosecurity interceptions. Here, a novel approach is taken to evaluate the potential for provenance resolution of insect samples through multiple biogeochemical markers. The international pest, Helicoverpa armigera, has been used as a model species to assess the validity of using naturally occurring δ2H, 87Sr/86Sr, 207Pb/206Pb and 208Pb/206Pb isotope ratios and trace element concentration signatures from single moth specimens for regional assignment to natal origin. None of the biogeochemical markers selected were individually able to separate moths from the different experimental regions (150–3000 km apart). Conversely, using multivariate analysis, the region of origin was correctly identified for approximately 75% of individual H. armigera samples. The geographic resolution demonstrated with this approach has considerable potential for biosecurity as well as other disciplines including forensics, ecology and pest management.

Modified sugar adulteration test applied to New Zealand honey

The carbon isotope method (AOAC 998.12) compares the bulk honey carbon isotope value with that of the extracted protein; a difference greater than 1‰ suggesting that the protein and the bulk carbohydrate have different origins. New Zealand Manuka honey is a high value product and often fails this test. It has been suggested such failures are due to the pollen in the Manuka honey and an adaptation of the method to remove pollen prior to testing has been proposed. Here we test 64 authentic honey samples collected directly from the hives and find that a large proportion (37%) of Manuka honeys fail the test. Of these 60% still fail the adapted method. These honey samples were collected and processed under stringent conditions and have not been adulterated post-harvest. More work is required to ascertain the cause of these test failures.

Rayleigh distillation equations applied to isotopic evolution of organic nitrogen across a continental shelf

The isotope enrichment of nitrate due to uptake by phytoplankton has previously been measured in a variety of ways, both in the field over time or space, and in vitro. This study provided an unusual opportunity to measure the isotopic fractionation of nitrate over an extended spatial scale. Results are presented from the Otago Continental shelf, New Zealand. δ15N-PON and [NO3–] was correlated using Rayleigh distillation equations to obtain isotope enrichment factors for the uptake of nitrate. The decrease in nitrate concentration during advection landward across the shelf was consistent with removal by phytoplankton, with an average enrichment factor (ϵ) of 8.2 per mil, as calculated using the Rayleigh accumulated product equation. The spatial evolution of δ15N-PON and [NO3–] across the Otago continental shelf led to the conclusion that cross-shelf advection is the predominant process bringing nutrients to the shelf. No Rayleigh distillation-type process is observable from monthly observations. However, in subantarctic surface water (SASW), a seasonal variation in δ15N-PON was seen that was in the opposite phase to that expected for isotopic enrichment of the nutrient pool. In SASW, δ15N-PON peaked at 4‰ in winter months and fell to –2‰ in the spring and summer.

Assessing Carbon and Hydrogen Isotopic Fractionation of Diesel Fuel n-alkanes During Progressive Evaporation

Compound‐specific isotope analysis offers potential for fingerprinting of diesel fuels, however, possible confounding effects of isotopic fractionation due to evaporation need to be assessed. This study measured the fractionation of the stable carbon and hydrogen isotopes in n‐alkane compounds in neat diesel fuel during evaporation. Isotope ratios were measured using a continuous flow gas chromatograph/isotope ratio mass spectrometer. Diesel samples were progressively evaporated at 24 ± 2°C for 21 days. Increasing depletion of deuterium in nC12–nC17 alkanes in the remaining liquid with increasing carbon chain length was observed. Negligible carbon isotope fractionation was observed. Preferential vaporization was measured for the shorter chain n‐alkanes and the trend decreased with increasing chain length. The decrease in δ2H values indicates the preferential vaporization of the isotopically heavier species consistent with available quantitative data for hydrocarbons. These results are most important in the application of stable isotope technology to forensic analysis of diesel.

Preparation of aqueous fatty acids for hydrogen and carbon stable isotope analysis by solid phase extraction

Stable isotope analyses of fatty acids in environmental waters provides important information as to their source(s). Analysis is often confounded due to low concentrations of fatty acids and/or a complex sample matrix requiring separationofthe target analyte.The purposeofthis study wastovalidatea methodtoextract fattyacidsfromnatural waters using solid phase extraction (SPE) before compound specific isotope analysis (CSIA). Three SPE cartridges and multiple eluting solvents were tested to determine the efficiency, isotopic fractionation, and reproducibility of each extraction technique. Our results indicated that surface-modified styrene divinylbenzene cartridges, when eluted with methanol, caused negligible fractionation of the hydrogen isotopes and minimal fractionation of the carbon isotopes, but that isotopic fractionation occurred when compounds were only partially eluted from SPE cartridges. Compounds were also extracted from landfill leachate using both SPE and liquid-liquid extraction (LLE). The hydrogen isotope composition (d 2 H) of compounds extracted from water using either method were within experimental precision and the carbon isotope composition (d 13 C) of all but one fatty acid were within experimental precision. Therefore, these experiments prove the aforementionedSPEmethods tobeaconvenient andprecisemethodtoextract fatty acidsfromnatural watersbeforeCSIA.