Evaluating the Application of Portable Handheld X-ray Fluorescence (XRF) Scanner for Determining Seafood Provenance: A Case Study on Penaeus monodon.

Seafood elemental profiling (SEP) is the quantification of a range of elements in seafood products and may serve in addressing questions of seafood provenance and quality. Traditional methods for analyzing soft tissue present several limitations for the industry-level use of SEP. Portable handheld X-ray fluorescence (pXRF) analysis is a promising alternative to conventional methods; however, its application for biological analysis has not been fully established. Intact giant tiger prawn (Penaeus monodon) abdomens were analyzed with a Vanta M series XRF portable analyzer following a novel soft tissue protocol. Exploratory statistics (principal component analysis, nonmetric multidimensional scaling, and canonical discriminant analysis), as well as random forest models, have been implemented with pXRF profiles, yielding 81% accuracy when assigning the geographical origin of P. monodon. The results of this study highlight that SEP via pXRF is a viable industry-level analysis, and its application will depend on improved instrument calibration to account for fluctuating wetness factors that are influenced by cooking, storage, and other pre- and post-harvest treatments.

Developing a MySQL Database for the Provenance of Black Tiger Prawns (Penaeus monodon).

As the demand for seafood increases, so does the incidence of seafood fraud. Confirming provenance of seafood is important to combat fraudulent labelling but requires a database that contains the isotopic and elemental "fingerprints" of authentic seafood samples. Local isotopic and elemental databases can be scaled up or combined with other databases to increase the spatial and species coverage to create a larger database. This study showcases the use of isotopic and elemental fingerprints of the black tiger prawn (Penaeus monodon) to develop a database that can be used to securely store the data necessary for determining provenance. The utility of this database was tested through querying and building seven different datasets that were used to develop models to determine the provenance of P. monodon. The models built using the data retrieved from the database demonstrated that the provenance of P. monodon could be determined with >80% accuracy. As the database was developed using MySQL, it can be scaled up to include additional regions, species, or methodologies depending on the needs of the users. Combining the database with methods of determining provenance will provide regulatory bodies and the seafood industry with another provenance tool to combat fraudulent seafood labelling.

Chronostratigraphy of sediment cores from Lake Selina, southeastern Australia: Radiocarbon, optically stimulated luminescence, paleomagnetism, authigenic beryllium isotopes and elemental data.

This Data in Brief paper comprises dataset obtained for sediment cores collected from Lake Selina, located in the West Coast Range of Tasmania, Australia. Datasets include radiocarbon and optically stimulated luminescence age estimates, elemental composition, beryllium isotopes, magnetic properties and the paleomagnetic record measured on the cores assigned as TAS1402 (Location: Tasmania, Year: 2014, Site number: 02). The multi-proxy dataset was used to develop a chronostratigraphy for the 5.5 m and 270,000 year old record. See Lisé-Pronovost et al. (2021) (10.1016/j.quageo.2021.101152) for interpretation and discussion. The data presented in this study serve as an archive for future studies focusing on Earth system dynamics and the timeline and linkages of environmental changes across Tasmania, the Southern Hemisphere and at a global scale.

Rare earth elements and yttrium as tracers of waste/rock-groundwater interactions.

Increasing concentrations of Rare Earth Elements (REE) plus yttrium (REY) are entering the environment due to human activities. The similar chemical behaviour across the whole REY, i.e. the lanthanide series (lanthanum to lutetium) and yttrium, allows their use as tracers, fingerprinting rock-forming processes and fluid-rock interactions in earth science systems. However, their use in fingerprinting waste and particularly low-level radioactive waste has not received much attention, despite the direct use of REE in the nuclear industry and the traditional use of REE as proxies to understand the environmental mobility of the actinide series (actinium to lawrencium). The highly instrumented low-level radioactive waste site at Little Forest (Australia) allows a detailed REY study, investigating interactions with local strata, neighbouring waste forms and shallow groundwater flows. Groundwater samples and solids from cored materials were recovered from 2007 to 2012 from the study site and regional baseline sites in the same geological materials. The REY in water samples were analysed by automated chelation pre-concentration (SeaFast, ESI) followed by ICP-MS determination, while solid samples were analysed using Neutron Activation Analysis (NAA) and X-ray fluorescence scanning (ITRAX). Solid rocks showed no REY departed from typical Upper Crust compositions in either Little Forest or regional background sites. Shallow groundwater from ~4-5 m, at or slightly below waste trench levels, showed water-waste interaction as a marked enrichment, relative to shale-normalised patterns, in samarium, europium and gadolinium, with depleted yttrium. Leachate samples from the neighbouring urban landfill show different REY normalised patterns. REY distribution changes with depth through increased interaction with shales and sandstones. Variations in pH and redox conditions lead to widespread precipitation of Fe-hydroxides, which scavenge REY with differential uptake by precipitating solids, resulting in increases in Y and higher Y/Ho ratio in the groundwater along the flow path. Our study revealed that the Little Forest low-level radioactive waste has a REY fingerprint different to that of groundwater in surrounding land uses. REY can be used to fingerprint diverse waste sources, assess the mobility of lanthanides inferring the mobility of selected actinides, and to trace the fate of REY during groundwater recharge. The approach presented can refine source allocation and trace pollutant mobility in current and legacy urban, mixed and radioactive waste sites around the world.

Tracking the provenance of octopus using isotopic and multi-elemental analysis.

Octopus play an increasingly important role in ocean ecosystems and global fisheries, yet techniques for authenticating provenance are sorely lacking. For the first time, we investigate whether chemical profiling can distinguish geographical origins of octopus on international and domestic scales. Our samples consisted of wild-caught octopus from south-east Asia and southern Australia, regions with high seafood trade. We used a novel combination of stable carbon (δ13C) and oxygen (δ18O) isotope analyses (Isotope-Ratio Mass Spectrometry) of internal calcified structures called statoliths, with elemental analyses (X-Ray Fluorescence using Itrax) of soft-tissue. We found that multivariate profiles exhibited distinctive regional signatures, even across species, with high classification success (∼95%) back to region of origin. This study validates isotopic and multi-elemental profiling as an effective provenance tool for octopus, which could be used to support transparency and accountability of seafood supply chains and thus encourage sustainable use of ocean resources.

Macro-charcoal accumulation in floodplain wetlands: Problems and prospects for reconstruction of fire regimes and environmental conditions.

Floodplain wetland ecosystems respond dynamically to flooding, fire and geomorphological processes. We employed a combined geomorphological and environmental proxy approach to assess allochthonous and autochthonous macro-charcoal accumulation in the Macquarie Marshes, Australia, with implications for the reconstruction of fire regimes and environmental conditions in large, open-system wetlands. After accounting for fluvial macro-charcoal flux (1.05 ± 0.32 no. cm-2 a-1), autochthonous macro-charcoal in ~1 m deep sediment profiles spanning ~1.7 ka were highly variable and inconsistent between cores and wetlands (concentrations from 0 to 438 no. cm-3, mean accumulation rates from 0 to 3.86 no. cm-2 a-1). A positive correlation existed between the number of recent fires, satellite-observed ignition points, and macro-charcoal concentrations at the surface of the wetlands. Sedimentology, geochemistry, and carbon stable isotopes (δ13C range -15 to -25 ‰) were similar in all cores from both wetlands and varied little with depth. Application of macro-charcoal and other environmental proxy techniques is inherently difficult in large, dynamic wetland systems due to variations in charcoal sources, sediment and charcoal deposition rates, and taphonomic processes. Major problems facing fire history reconstruction using macro-charcoal records in these wetlands include: (1) spatial and temporal variations in fire activity and ash and charcoal products within the wetlands, (2) variations in allochthonous inputs of charcoal from upstream sources, (3) tendency for geomorphic dynamism to affect flow dispersal and sediment and charcoal accumulation, and (4) propensity for post-depositional modification and/or destruction of macro-charcoal by flooding and taphonomic processes. Recognition of complex fire-climate-hydrology-vegetation interactions is essential. High-resolution, multifaceted approaches with reliable geochronologies are required to assess spatial and temporal patterns of fire and to reconstruct in order to interpret wetland fire regimes.

Impacts of land reclamation on tidal marsh 'blue carbon' stocks.

Tidal marsh ecosystems are among earth's most efficient natural organic carbon (C) sinks and provide myriad ecosystem services. However, approximately half have been 'reclaimed' - i.e. converted to other land uses - potentially turning them into sources of greenhouse gas emissions. In this study, we applied C stock measurements and paleoanalytical techniques to sediments from reclaimed and intact tidal marshes in southeast Australia. We aimed to assess the impacts of reclamation on: 1) the magnitude of existing sediment C stocks; 2) ongoing C sequestration and storage; and 3) C quality. Differences in sediment horizon depths (indicated by Itrax-XRF scanning) and ages (indicated by lead-210 and radiocarbon dating) suggest a physical loss of sediments following reclamation, as well as slowing of sediment accumulation rates. Sediments at one meter depth were between ~2000 and ~5300 years older in reclaimed cores compared to intact marsh cores. We estimate a 70% loss of sediment C in reclaimed sites (equal to 73 Mg C ha-1), relative to stocks in intact tidal marshes during a comparable time period. Following reclamation, sediment C was characterized by coarse particulate organic matter with lower alkyl-o-alkyl ratios and higher amounts of aromatic C, suggesting a lower extent of decomposition and therefore lower likelihood of being incorporated into long-term C stocks compared to that of intact tidal marshes. We conclude that reclamation of tidal marshes can diminish C stocks that have accumulated over millennial time scales, and these losses may go undetected if additional analyses are not employed in conjunction with C stock estimates.

Itrax micro X-ray fluorescence (µXRF) for soft biological tissues.

Determination of the elemental composition of soft biological tissue is a time-consuming and tedious process when using traditional analytical techniques. In this method, micro X-ray fluorescence (µXRF) via Itrax, a scanning instrument, was used to determine elemental abundance at a resolution of 200 µm. Itrax µXRF was initially designed for elemental profiling of geological cores, and the capability of this technique was extended to soft biological tissue samples. The samples were dried and ground into a fine powder before analysis. The scanner generates elemental values as counts per 1 mm and these values are standardised to obtain the relative elemental abundance of the elements present in the samples. The acquired data can be used for environmental and biological research. •No literature could be found whereby the capability of Itrax µXRF has been extended to soft biological tissue samples.•The major advantages Itrax has over conventional methods is that it is a simultaneous technique which allows data to be acquired for over 30 elements at once with minimal sample preparation.•It is a non-destructive process where the samples can be re-used for additional analyses if necessary; this is especially useful when there is only a limited amount of sample available for other analyses.

Novel detection of provenance in the illegal wildlife trade using elemental data.

Despite being the fourth largest criminal market in the world, no forensic tools have been sufficiently developed to accurately determine the legal status of seized animals and their parts. Although legal trading is permissible for farmed or captive-bred animals, many animals are illegally removed from the wild and laundered by masquerading them as captive bred. Here we present high-resolution x-ray fluorescence (XRF) as a non-invasive and cost-effective tool for forensic classification. We tested the efficacy of this technique by using machine learning on a training set of zoo specimens and wild-caught individuals of short-beaked echidnas (Tachyglossus aculeatus), a small insectivorous monotreme in Australia. XRF outperformed stable isotope analysis (δ13C, δ15N), reducing overall classification error below 4%. XRF has the added advantage of providing samples every 200 µm on a single quill, enabling 100% classification accuracy by taking the consensus of votes per quill. This accurate and cost-effective forensic technique could provide a much needed in situ solution for combating the illegal laundering of wildlife, and conversely, assist with certification of legally bred animals.

Identifying heavy metal levels in historical flood water deposits using sediment cores.

When designing mitigation and restoration strategies for aquatic systems affected by heavy metal contamination, we must first understand the sources of these pollutants. In this study, we introduce a methodology that identifies the heavy metal levels in floodplain lake sediments deposited by one source; fluvial floods. This is done by comparing sediment core heavy metal profiles (i.e., historical pollution trends) to physical and chemical properties of sediments in these cores (i.e., historical flooding trends). This methodology is applied to Willsmere and Bolin Billabongs, two urban floodplain lakes (billabongs) of the Yarra River (South-East Australia). Both billabongs are periodically inundated by flooding of the Yarra River and one billabong (Willsmere Billabong) is connected to an urban stormwater drainage network. 1-2-m long sediment cores (containing sediment deposits up to 500 years old) were taken from the billabongs and analysed for heavy metal concentrations (arsenic, chromium, copper, lead, nickel, zinc). In cores from both billabongs, arsenic concentrations are high in the flood-borne sediments. In Bolin Billabong, absolute metal levels are similar in flood and non-flood deposits. In Willsmere Billabong, absolute copper, lead and zinc levels were generally lower in fluvial flood-borne sediments in the core compared to non-fluvial sediments. This suggests that heavy metal concentrations in Bolin Billabong sediments are relatively similar regardless of whether or not fluvial flooding is occurring. However for Willsmere Billabong, heavy metal concentrations are high when overland runoff, direct urban stormwater discharges or atmospheric deposition is occurring. As such, reducing the heavy metal concentrations in these transport pathways will be of great importance when trying to reduce heavy metal concentrations in Willsmere Billabong sediments. This study presents a proof-of-concept that can be applied to other polluted aquatic systems, to understand the importance of river floods in the contamination of the bed sediments of aquatic systems. As a cost effective and less time consuming alternative to extensive field monitoring, our proposed method can be used to identify the key sources of pollution and therefore support the development of effective management strategies.

Sediment cores as archives of historical changes in floodplain lake hydrology.

Anthropogenic activities are contributing to the changing hydrology of rivers, often resulting in their degradation. Understanding the drivers and nature of these changes is critical for the design and implementation of effective mitigation strategies for these systems. However, this can be hindered by gaps in historical measured flow data. This study therefore aims to use sediment cores to identify historical hydrological changes within a river catchment. Sediment cores from two floodplain lakes (billabongs) in the urbanised Yarra River catchment (Melbourne, South-East Australia) were collected and high resolution images, trends in magnetic susceptibility and trends in elemental composition through the sedimentary records were obtained. These were used to infer historical changes in river hydrology to determine both average trends in hydrology (i.e., coarse temporal resolution) as well as discrete flood layers in the sediment cores (i.e., fine temporal resolution). Through the 20th century, both billabongs became increasingly disconnected from the river, as demonstrated by the decreasing trends in magnetic susceptibility, particle size and inorganic matter in the cores. Additionally the number of discrete flood layers decreased up the cores. These reconstructed trends correlate with measured flow records of the river through the 20th century, which validates the methodology that has been used in this study. Not only does this study provide evidence on how natural catchments can be affected by land-use intensification and urbanisation, but it also introduces a general analytical framework that could be applied to other river systems to assist in the design of hydrological management strategies.