Christopher M. Wurster

Algal biochar – production and properties

This study presents baseline data on the physiochemical properties and potential uses of macroalgal (seaweed) biochar produced by pyrolysis of eight species of green tide algae sourced from fresh, brackish and marine environments. All of the biochars produced are comparatively low in carbon content, surface area and cation exchange capacity, but high in pH, ash, nitrogen and extractable inorganic nutrients including P, K, Ca and Mg. The biochars are more similar in characteristics to those produced from poultry litter relative to those derived from ligno-cellulosic feedstocks. This means that, like poultry litter biochar, macroalgal biochar has properties that provide direct nutrient benefits to soils and thereby to crop productivity, and will be particularly useful for application on acidic soils. However, macroalgal biochars are volumetrically less able to provide the carbon sequestration benefits of the high carbon ligno-cellulosic biochars.

Forest contraction in north equatorial Southeast Asia during the Last Glacial Period

Today, insular Southeast Asia is important for both its remarkably rich biodiversity and globally significant roles in atmospheric and oceanic circulation. Despite the fundamental importance of environmental history for diversity and conservation, there is little primary evidence concerning the nature of vegetation in north equatorial Southeast Asia during the Last Glacial Period (LGP). As a result, even the general distribution of vegetation during the Last Glacial Maximum is debated. Here we show, using the stable carbon isotope composition of ancient cave guano profiles, that there was a substantial forest contraction during the LGP on both peninsular Malaysia and Palawan, while rainforest was maintained in northern Borneo. These results directly support rainforest “refugia” hypotheses and provide evidence that environmental barriers likely reduced genetic mixing between Borneo and Sumatra flora and fauna. Moreover, it sheds light on possible early human dispersal events.

Punctuated eustatic sea-level rise in the early mid-Holocene

Whether eustatic sea-level rise through the Holocene has been punctuated or continuous has remained controversial for almost two decades. Resolving this debate has implications for predicting future responses of remaining ice sheets to climate change and also for understanding the drivers of human settlement and dispersal patterns through prehistory. Here we present a sea-level curve for the past 8900 yr from Singapore, a tectonically stable location remote from ice-loading effects. We also present critical and unique sedimentation rate, organic δ13C, and foraminiferal δ13C proxy records of sea-level change derived from a shallow-marine sediment core from the same area over the same time interval. The sea-level curve, corroborated by the independent proxy records, suggests rapid rise at a rate of 1.8 m/100 yr until 8100 cal (calibrated) yr B.P., a near cessation in the rate of sea-level rise between 7800 and 7400 cal yr B.P., followed by a renewed rise of 4–5 m that was complete by 6500 cal yr B.P. We suggest that this period of relatively stable sea level during the early to mid-Holocene enabled modern deltas to advance, providing a highly productive environment for the establishment of coastal sedentary agriculture. Periods of rapid sea-level rise before and after may have catalyzed significant postglacial episodes of human dispersal in coastal regions.

Advances in micromilling techniques: a new apparatus for acquiring high—resolution oxygen and carbon stable isotope values and major/minor elemental ratios from accretionary carbonate

A computer-controlled micromilling apparatus that permits discrete sampling of accretionary biogenic carbonate specimens with micron-scale resolution has been developed for the purpose of acquiring high-resolution δ13C and δ18O values, and major/minor elemental chemistry. Secular variation in stable isotope ratios and major/minor elemental composition records inter-annual and intra-annual changes in the environmental parameters or animal behavior for extant and extinct species. A polished specimen is attached to a stage beneath a fixed micro-milling head, and viewed on a large-screen monitor via a color digital camera. Growth bands (analogous to tree rings) are generally a result of variable accretion rates in biogenic carbonates. These growth features are first digitized in real-time as a series of three-dimensional coordinates. To better characterize complex growth features, intermediate coordinates are interpolated using a cubic spline fit through the digital points. Intermediate sampling paths, which mimic less visible daily growth banding, are in turn calculated between digitized curves. Sampling path arrays serve to guide three high precision actuators, which position the sample stage relative to the fixed micromilling head. A fourth actuator provides vertical control of the digital color camera (compensating for vertical movement of the z-axis stage actuator) keeping the specimen image focused. This new micromilling device permits high-resolution sampling of complex internal structures via a user-friendly program interface.

Algal biochar: effects and applications

Algae represent a promising target for the generation of bioenergy through slow pyrolysis, leading to the production of biochar. This study reports experiments conducted on the production of freshwater and saltwater macroalgal biochar in pilot‐scale quantities, the physical and chemical characteristics of the biochars, and their impact on plant growth. The biochars are low in carbon (C) content, surface area and cation exchange capacity, while being high in ash and nutrients. Trace element analysis demonstrates that macroalgal biochar produced from unpolluted water does not contain toxic trace elements in excess of levels mandated for unrestricted use as a biosolids amendment to soils. Pot trials conducted using a C and nutrient‐poor soil, without and with additional fertilizer, demonstrate dramatic increases between 15 and 32 times, respectively, in plant growth rate for biochar treatments compared with the no biochar controls, with additional smaller increases when fertilizer was added. Pot trials conducted using a relatively fertile agricultural soil showed smaller but significant impacts of biochar amendment over the controls.

Metabolic rate of late Holocene freshwater fish: evidence from δ13C values of otoliths

Abstract We examine patterns of intra-otolith variation in δ13C values of fossil Aplodinotus grunniens (freshwater drum) otoliths recovered from an archeological site in northeast Tennessee. We find three repeatable patterns: an initial increase early in ontogeny followed by relatively stable δ13C values as the fish ages, an initial strong covariation between seasonal δ18O and δ13C values, and a decrease with age in the magnitude of seasonal change in δ13C values. These last two observations are illustrated by seasonal least-squares linear regressions between δ13C and δ18O values that tend to progressively decrease in r2 value and slope with fish age. These patterns are evaluated by using a mass balance model in which otolith δ13C values are derived from dissolved inorganic carbon of ambient water mixing with carbon derived from metabolic processes. The proportion of metabolically derived carbon is found to be the dominant factor controlling intra-otolith variation in δ13C values. Thus, the difference between maximum and minimum δ13C values from a single otolith (δ13Cmax–min) is postulated to reflect the total change in metabolic rate over the lifetime of a fish. δ13Cmax–min values significantly and negatively covary with average δ18O(CaCO3) values, suggesting either a higher total change in metabolic rate over the lifetime of a fish in cooler climates characterized by shorter growing seasons, or a decrease in summer/winter precipitation ratio. A proxy for metabolic rate preserved in otoliths would facilitate the understanding of evolutionary history in physiological traits of fishes and improve our understanding of bioenergetics.

Stable carbon and hydrogen isotopes from bat guano in the Grand Canyon, USA, reveal Younger Dryas and 8.2 ka events

We inferred climate change through the Pleistocene-Holocene transition from δ 13 C and δD values of bat guano deposited from 14.5 to 6.5 ka (calendar ka) in Bat Cave, Grand Canyon, Arizona. The δ 13 C and δD values generally covaried, indicating that regional late Pleistocene climate was relatively cool and wet, and early Holocene climate gradually became warmer with increased summer precipitation until ca. 9 ka, at which time the onset of modern North American Monsoon–like conditions occurred. During the Younger Dryas event, δ 13 C values decreased, whereas δD values increased, indicating a cool and possibly drier period. We also observed a distinct isotopic anomaly during the 8.2 ka event, at which time both δ 13 C and δD values decreased. The δ 13 C values abruptly increased at 8.0 ka, suggesting a rapid change in atmospheric circulation and greater infl uence from convective storms originating from the south. Deposits of bat guano represent a largely untapped source of paleoenvironmental information that can provide continuous and long-term continental archives of environmental change.

Seasonal variation in stable oxygen and carbon isotope values recovered from modern lacustrine freshwater mollusks: paleoclimatological implications for sub-weekly temperature records

A fingernail clam (Sphaerium simile, Sphaeriidae) from Science Lake, a small watershed located in Allegany State Park, New York, USA and a zebra mussel (Dreissena polymorpha, Dreissenidae) from Keuka Lake, New York, the third largest Finger Lake of central New York, were selected to evaluate the applicability of using δ18O(CaCO3) and δ13O(CaCO3) values for sub-weekly climate records. Seasonal variation in δ18O(CaCO3) values was compared with predicted equilibrium values to test the hypothesis that lacustrine molluscs produce shell aragonite according to environmental variables. For the purpose of comparison, aragonite temperature-fractionation equations determined by Grossman& Ku (1986) and Patterson et al. (1993) were used. Sphaerium simile appears to produce δ18O(CaCO3) values predicted by Patterson et al. (1993), while Dreissena polymorpha produces δ18O(CaCO3) values in agreement with Grossman & Ku (1986). We attribute the difference to family-specific temperature-fractionation relationships. Because both types of mollusc record climate variables with a high degree of integrity, they should each serve as excellent paleoclimate proxies.The fingernail clam collected from a small watershed exhibits higher variation about the seasonal pattern than did the zebra mussel collected from a large watershed. This is attributed to the increased sensitivity of the small watershed to storm perturbation. Analysis of fossil molluscs from such watersheds might be useful in discerning paleo-storminess.

Comparison of secondary ion mass spectrometry and micromilling/continuous flow isotope ratio mass spectrometry techniques used to acquire intra‐otolith δ18O values of wild Atlantic salmon (Salmo salar)

The chemical signals in the sequential layers of fish otoliths have the potential to provide fisheries biologists with temporal and spatial details of migration which are difficult to obtain without expensive tracking methods. Signal resolution depends, however, on the extraction technique used. We compared the use of mechanical micromilling and continuous flow isotope ratio mass spectrometry (CF-IRMS) methods with secondary ion mass spectrometry (SIMS) to obtain delta(18)O profiles from otoliths of wild Atlantic salmon (Salmo salar) and used these to corroborate the time of freshwater emigration of the juvenile with macroscopic patterns within the otolith. Both techniques showed the transition occurring at the same visible feature on the otolith, allowing future analyses to easily identify the juvenile (freshwater) versus adult (marine) life-stages. However, SIMS showed a rapid and abrupt transition whereas micromilling provided a less distinct signal. The number of samples that could be obtained per unit area sampled using SIMS was 2 to 3 times greater than that when using micromilling/CF-IRMS although the delta(18)O values and analytical precisions (approximately 0.2 per thousand) of the two methods were comparable. In addition, SIMS delta(18)O results were used to compare otolith aragonite values with predicted values calculated using various isotope fractionation equations.

Microwave extraction-isotope ratio infrared spectroscopy (ME-IRIS): a novel technique for rapid extraction and in-line analysis of δ18O and δ2H values of water in plants, soils and insects.

RATIONALE Traditionally, stable isotope analysis of plant and soil water has been a technically challenging, labour-intensive and time-consuming process. Here we describe a rapid single-step technique which combines Microwave Extraction with Isotope Ratio Infrared Spectroscopy (ME-IRIS). METHODS Plant, soil and insect water is extracted into a dry air stream by microwave irradiation within a sealed vessel. The water vapor thus produced is carried to a cooled condensation chamber, which controls the water vapor concentration and flow rate to the spectrometer. Integration of the isotope signals over the whole analytical cycle provides quantitative δ(18)O and δ(2) H values for the initial liquid water contained in the sample. Calibration is carried out by the analysis of water standards using the same apparatus. Analysis of leaf and soil water by cryogenic vacuum distillation and IRMS was used to validate the ME-IRIS data. RESULTS Comparison with data obtained by cryogenic distillation and IRMS shows that the new technique provides accurate water isotope data for leaves from a range of field-grown tropical plant species. However, two exotic nursery plants were found to suffer from spectral interferences from co-extracted organic compounds. The precision for extracted leaf, stem, soil and insect water was typically better than ±0.3 ‰ for δ(18)O and ±2 ‰ for δ(2) H values, and better than ±0.1 ‰ for δ(18)O and ±1 ‰ for δ(2) H values when analyzing water standards. The effects of sample size, microwave power and duration and sample-to-sample memory on isotope values were assessed. CONCLUSIONS ME-IRIS provides rapid and low-cost extraction and analysis of δ(18)O and δ(2) H values in plant, soil and insect water (≈10-15 min for samples yielding ≈ 0.3 mL of water). The technique can accommodate whole leaves of many plant species.