Search

Background: Cardiology training is demanding and associated with high workloads. Poor lifestyle and health among clinicians may stretch workforces and impact patient care. It has not been established what impact training in cardiology has on the doctors undertaking it. We aimed to establish the prevalence of physical and mental illness, burnout and the ability to maintain a healthy lifestyle among cardiology trainees in the United Kingdom (UK)., Methods: The 2023 British Junior Cardiologists' Association training survey included questions on ill health, burnout, healthy living and invited responders to complete screening questionnaires for depression (Patient Health Questionnaire 9; PHQ-9) and anxiety (Generalised Anxiety Disorder 7; GAD-7). Significant anxiety and depression were defined as scoring within the moderate or severe range (PHQ-9≥10; GAD-7≥10). Burnout was a self-reported outcome. Poisson regression was used to determine prevalence ratios (PR) between univariate predictors of anxiety, depression and burnout., Results: Of 398 responders, 212 consented to answer health and well-being questions. Prior physical and mental health conditions were reported by 9% and 7% of trainees, respectively. Significant depression and anxiety symptoms were reported by 25% and 18% of trainees, respectively. Burnout was reported by 76% of trainees. Less than full-time trainees reported greater anxiety (PR 2.92, 95% CI 1.39 to 6.16, p<0.01) and depression (PR 3.66, 95% CI 2.24 to 5.98, p<0.01), while trainees with dependents reported less burnout (PR 0.77, 95% CI 0.65 to 0.92, p<0.01). Exercise, good sleep quality and maintaining a healthy diet were associated with less burnout and depressive symptoms (p<0.05). Half of trainees reported training having a negative impact on well-being, driven by the amount of service provision, curriculum requirements and lack of training opportunities., Conclusions: The prevalence of anxiety, depression and burnout is high among UK cardiology trainees. Further work should establish the impact of cardiology trainee health on the quality of patient care. Training bodies should consider how occupational factors may contribute to health., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2024. No commercial re-use. See rights and permissions. Published by BMJ.)

Expert judgment underpins assessment of threatened ecosystems. However, experts are often narrowly defined, and variability in their judgments may be substantial. Models built from structured elicitation with large diverse expert panels can contribute to more consistent and transparent decision-making. We conducted a structured elicitation under a broad definition of expertise to examine variation in judgments of ecosystem viability and collapse in a critically endangered ecosystem. We explored whether variation in judgments among 83 experts was related to affiliation and management expertise and assessed performance of an average model based on common ecosystem indicators. There were systematic differences among individuals, much of which were not explained by affiliation or expertise. However, of the individuals affiliated with government, those in conservation and environmental departments were more likely to determine a patch was viable than those in agriculture and rural land management. Classification errors from an average model, in which all individuals were weighted equally, were highest among government agriculture experts (27%) and lowest among government conservation experts (12%). Differences were mostly cases in which the average model predicted a patch was viable but the individual thought it was not. These differences arose primarily for areas that were grazed or cleared of mature trees. These areas are often the target of restoration, but they are also valuable for agriculture. These results highlight the potential for conflicting advice and disagreement about policies and actions for conserving and restoring threatened ecosystems. Although adoption of an average model can improve consistency of ecosystem assessment, it can fail to capture and convey diverse opinions held by experts. Structured elicitation and models of ecosystem viability play an important role in providing data-driven evidence of where differences arise among experts to support engagement and discussion among stakeholders and decision makers and to improve the management of threatened ecosystems., (© 2024 State of New South Wales. Conservation Biology published by Wiley Periodicals LLC on behalf of Society for Conservation Biology.)

Identifying threatened ecosystem types is fundamental to conservation and management decision-making. When identification relies on expert judgment, decisions are vulnerable to inconsistent outcomes and can lack transparency. We elicited judgements of the occurrence of a widespread, critically endangered Australian ecosystem from a diverse pool of 83 experts. We asked 4 questions. First, how many experts are required to reliably conclude that the ecosystem is present? Second, how many experts are required to build a reliable model for predicting ecosystem presence? Third, given expert selection can narrow the range opinions, if enough experts are selected, do selection strategies affect model predictions? Finally, does a diverse selection of experts provide better model predictions? We used power and sample size calculations with a finite population of 200 experts to calculate the number of experts required to reliably assess ecosystem presence in a theoretical scenario. We then used boosted regression trees to model expert elicitation of 122 plots based on real-world data. For a reliable consensus (90% probability of correctly identifying presence and absence) in a relatively certain scenario (85% probability of occurrence), at least 17 experts were required. More experts were required when occurrence was less certain, and fewer were needed if permissible error rates were relaxed. In comparison, only ∼20 experts were required for a reliable model that could predict for a range of scenarios. Expert selection strategies changed modeled outcomes, often overpredicting presence and underestimating uncertainty. However, smaller but diverse pools of experts produced outcomes similar to a model built from all contributing experts. Combining elicited judgements from a diverse pool of experts in a model-based decision support tool provided an efficient aggregation of a broad range of expertise. Such models can improve the transparency and consistency of conservation and management decision-making, especially when ecosystems are defined based on complex criteria., (© 2023 Society for Conservation Biology.)

The trustworthiness of a system is not just about proving the identity or integrity of the hardware but also extends to the data, control, and management planes of communication between devices and the software they are running. This trust in data and device integrity is desirable for Internet of Things (IoT) systems, especially in critical environments. In this study, we developed a security framework, IoTAttest, for building IoT systems that leverage the Trusted Platform Module 2.0 and remote attestation technologies to enable the establishment of IoT devices' collected data and control plan traffic integrity. After presenting the features and reference architecture of IoTAttest, we evaluated the privacy preservation and validity through the implementation of two proof-of-concept IoT applications that were designed by two teams of university students based on the reference architecture. After the development, the developers answered open questions regarding their experience and perceptions of the framework's usability, limitations, scalability, extensibility, potential, and security. The results indicate that IoTAttest can be used to develop IoT systems with effective attestation to achieve device and data integrity. The proof-of-concept solutions' outcomes illustrate the functionalities and performance of the IoT framework. The feedback from the proof-of-concept developers affirms that they perceived the framework as usable, scalable, extensible, and secure.

The clarification of drinking water leads to the production of large quantities of water treatment residuals (WTRs). DNA was extracted from six WTR samples collected from water treatment plants within the UK to compare their bacterial communities and examine whether factors such as coagulant usage (aluminium versus iron salt), the type of water source (reservoir or river), or leachable chemical composition influence these communities. Bacterial 16S variable region 4 (V4) was amplified and sequenced using Illumina MiSeq sequencing. The most abundant phyla in WTR samples were Proteobacteria, Actinobacteria, Bacteroidetes, Acidobacteria, and Firmicutes, collectively representing 92.77-97.8% of the total bacterial sequences. Statistical analysis of microbial profiles indicated that water source played a significant role in microbial community structure, diversity, and richness, however coagulant type did not. PERMANOVA analysis showed that no single chemical variable (pH, organic matter, or extractable element concentration) influenced microbial composition significantly; however, canonical correspondence analysis of WTR microbiomes yielded a model using all these variables that could be used to explain variations in microbial community structures of WTRs (p < 0.05). No common, potentially toxic cyanobacteria, or related pathogens of concern were found. Analysis with PICRUSt showed that WTRs all had similar predicted microbial functional profiles. Overall, the results indicate that WTRs analysed in this study are unlikely to pose any threat to soil microbial community structure when applied to land as a soil conditioner or enhancer and may help to enhance the soil microbial community., (© 2023. The Author(s).)

It is estimated that >400 Mt of board and paper are produced globally per year, and that 4.3-40 kg (dw) of sludge like material, pulp and paper mill sludge (PPMS), is generated for every tonne of product. PPMS are now more widely reused in agriculture as a soil amendment due to their high organic content of 40-50% by weight, perceived low toxicity and possible liming capabilities. Within this review article historic and recent literature on PPMS land spreading are combined with knowledge of European and UK regulation to explore the benefits, potential impacts and viability of land spreading PPMS. The review reveals that risks relating to potential N immobilisation in soils post-application can be readily mitigated, if desired, by coapplication of an N source, or even pre-treatment of sludge via composting. The benefits to crops have been demonstrated emphatically, while negative ecological impacts under typical field application rates have not been observed to date. The case is therefore strong for continued land application of the material as an environmentally responsible and sustainable use option. However, there are currently gaps in the literature regarding longer-term implications of PPMS applications in agriculture and in regards to the possible presence of emerging contaminants in some PPMS materials, both of which have been identified as areas that merit further research., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Human remains have been interred in burial grounds since historic times. Although the re-use of graveyards differs from one country, region or time period to another, over time, graveyard soil may become contaminated or enriched with heavy metal elements. This paper presents heavy metal element soil analysis from two UK church graveyard study sites with contrasting necrosols, but similar burial densities and known burial ages dating back to the sixteenth century and some possibly older than 1,000 years. Portable X-ray fluorescence element laboratory-based analyses were undertaken on surface and near-surface soil pellets. Results show elevated levels of Fe, Pb, Mn, Cr, Cu, Zn and Ca in both necrosols when compared with background values. Element concentration anomalies remained consistently higher than background samples down to 2 m, but reduced with distance away from church buildings. Element concentration anomalies are higher in the clay-rich necrosol than in sandy necrosol. Study result implications suggest that long-used necrosols are likely to be more contaminated with heavy metal elements than similar soil outside graveyards with implications for burial grounds management, adjacent populations and where burial grounds have been deconsecrated and turned to residential dwellings., (© 2022. The Author(s).)

Oxidative stress within the vascular endothelium, due to excess generation of reactive oxygen species (ROS), is thought to be fundamental to the initiation and progression of the cardiovascular complications of type 2 diabetes mellitus. The term ROS encompasses a variety of chemical species including superoxide anion (O 2 •- ), hydroxyl radical (OH - ) and hydrogen peroxide (H 2 O 2 ). While constitutive generation of low concentrations of ROS are indispensable for normal cellular function, excess O 2 •- can result in irreversible tissue damage. Excess ROS generation is catalysed by xanthine oxidase, uncoupled nitric oxide synthases, the mitochondrial electron transport chain and the nicotinamide adenine dinucleotide phosphate (NADPH) oxidases. Amongst enzymatic sources of O 2 •- the Nox2 isoform of NADPH oxidase is thought to be critical to the oxidative stress found in type 2 diabetes mellitus. In contrast, the transcriptionally regulated Nox4 isoform, which generates H 2 O 2 , may fulfil a protective role and contribute to normal glucose homeostasis. This review describes the key roles of Nox2 and Nox4, as well as Nox1 and Nox5, in glucose homeostasis, endothelial function and oxidative stress, with a key focus on how they are regulated in health, and dysregulated in type 2 diabetes mellitus.

Water-treatment residuals (WTRs), by-products of drinking water clarification, are increasingly recycled to land to promote circular economy and reduce disposal costs, yet there is a lack of published literature on their effects on soil ecology. In the present study, the effects of WTRs on earthworm growth, soil respiration, and soil porewater chemistry were investigated throughout a 7-wk outdoor mesocosm trial. We derived WTRs from both aluminum and iron coagulants and applied them to a loam soil at 0 to 20% (w/w). In addition, soil from a field that had received long-term WTR applications and that of an adjacent nontreated reference field were included in the study. Earthworm mass increase was significantly higher in all but one laboratory-treated soil when compared to the control. Furthermore, a linear regression model was used to predict increases in weekly soil respiration based on the application rates of both Al and Fe WTRs. In addition, a significant increase in soil respiration was observed from the treated farm soils during the first 4 wk of the trial. Measured sodium, magnesium, potassium, and iron porewater concentrations were higher in the treated farm soils than the reference site soil in a majority of samples, although these differences may be related to land management. Laboratory-treated soils had elevated porewater arsenic concentrations (e.g., ~17 µg L -1 in controls vs ~62 µg L -1 in the 20% w/w Al WTR treatment in week 1), whereas porewater nickel concentrations were, respectively, elevated and lowered in Al WTR- and Fe WTR-amended samples. Overall, observed disturbances to soil ecology were determined to be minimal. Environ Toxicol Chem 2021;40:1964-1972. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

There are thousands of disused and abandoned mining sites around the world with substantial accumulations of exposed mine spoil materials that pose a direct threat to their surrounding environment. Management of such sites, and neutralisation of the environmental threats they pose, is therefore extremely important and is an issue of global significance. Low cost management and remediation strategies need to be developed because many abandoned mine sites are in remote and/or economically challenged areas. One promising option is the incorporation of biochar into spoil materials, which has the potential to immobilise leachable toxic constituents and facilitate revegetation and thereby stabilisation of spoil heaps. This study investigated the capacity of readily available biochar materials made from wheat and rice waste products to immobilise and retain key metallic contaminants Pb and Zn from solution, and also investigated the utility of biochar application for remediating mine spoil heaps from different mine types in terms of facilitating establishment of vegetation coverage and minimising porewater element mobility within spoil heaps. The results demonstrated the high sorption capacity of the biochars (typically >97% of Pb or Zn in solution) and their ability to retain the metals despite an active desorption procedure (>93% of sorbed Pb retained and >75% of sorbed Zn). The remediation trial revealed that biochar application increased plant yield and decreased plant assimilation of many potentially toxic elements and also decreased spoil porewater concentrations of Al, Cd, Pb and Zn in most cases. In some spoil types investigated biochar addition also significantly decreased porewater concentrations of As (e.g. from ~30 mg/L to ~5 mg/L), demonstrating its potential utility for low cost environmental remediation across a range of mine spoil types., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Measuring the status and trends of biodiversity is critical for making informed decisions about the conservation, management or restoration of species, habitats and ecosystems. Defining the reference state against which status and change are measured is essential. Typically, reference states describe historical conditions, yet historical conditions are challenging to quantify, may be difficult to falsify, and may no longer be an attainable target in a contemporary ecosystem. We have constructed a conceptual framework to help inform thinking and discussion around the philosophical underpinnings of reference states and guide their application. We characterize currently recognized historical reference states and describe them as Pre-Human, Indigenous Cultural, Pre-Intensification and Hybrid-Historical. We extend the conceptual framework to include contemporary reference states as an alternative theoretical perspective. The contemporary reference state framework is a major conceptual shift that focuses on current ecological patterns and identifies areas with higher biodiversity values relative to other locations within the same ecosystem, regardless of the disturbance history. We acknowledge that past processes play an essential role in driving contemporary patterns of diversity. The specific context for which we design the contemporary conceptual frame is underpinned by an overarching goal-to maximize biodiversity conservation and restoration outcomes in existing ecosystems. The contemporary reference state framework can account for the inherent differences in the diversity of biodiversity values (e.g. native species richness, habitat complexity) across spatial scales, communities and ecosystems. In contrast to historical reference states, contemporary references states are measurable and falsifiable. This 'road map of reference states' offers perspective needed to define and assess the status and trends in biodiversity and habitats. We demonstrate the contemporary reference state concept with an example from south-eastern Australia. Our framework provides a tractable way for policy-makers and practitioners to navigate biodiversity assessments to maximize conservation and restoration outcomes in contemporary ecosystems., (© 2020 Commonwealth of Australia. Global Change Biology published by John Wiley & Sons Ltd.)

Biochar is the degradation-resistant product generated by the pyrolysis of organic materials and is produced for the intended use of land application in order to promote carbon sequestration and soil improvement. However, despite the many potential benefits biochar application offers, it is important to quantify any ecological impacts that may result from soil amendment in order to avoid potentially causing negative effects upon soil biota which are crucial in the many ecosystem services provided by soil. Any impacts on earthworms in particular are important to evaluate because of their pivotal role in organic matter breakdown, nutrient cycling and soil formation. In this study, we conducted a series of ecotoxicological assays to determine lethal and sublethal (avoidance, mass change and moisture content) effects of heavy biochar applications that reflect levels that may be used in soil restoration efforts. Two earthworm species, Eisenia fetida, an epigeic species, and Lumbricus terrestris, an anecic species, were utilised as test organisms. Two types of biochar, produced from wheat straw and rice husk feedstocks, respectively, were applied to OECD artificial soil and to a natural soil (Kettering loam) at rates of up to 20% w/w. The influence of biochar application on soil porewater chloride, fluoride and phosphate concentrations was also assessed. The biochar applications induced only a subtle level of avoidance behaviour while effects on survival over a 4-week exposure period were inconsistent. However, death and physical damage to some individual earthworms at high biochar application rates were observed, the mechanisms and processes leading to which should be investigated further. Earthworm development (mean mass change over time) proved to be a more sensitive measure, revealing negative effects on L. terrestris at 10% and 20% (w/w) wheat biochar applications in OECD soil and at 20% (w/w) applications of both biochars in Kettering loam. The moisture content of E. fetida remained remarkably consistent across all treatments (~ 82%), indicating that this is not a sensitive measure of effects. The high rates of biochar application resulted in increased chloride (2 to 3-fold) and phosphate (100-fold) concentrations in simulated soil porewaters, which has important implications for soil fertility and production but also for environmental management.

During clarification processes of raw water, a vast amount of by-product known as "drinking water-treatment residuals" (WTRs) are produced, being principally composed of hydroxides of the Al or Fe salts added during water treatment plus the impurities they remove. Aluminum-based (Al-WTR) and iron-based (Fe-WTR) materials were applied at 10% w/w to degraded, bare (unvegetated) soils from a restored coal mining site in central England (pH <3.9) to study their potential amelioration effects on earthworm mortality, biomass yield of seedling plants, and element concentrations in plant tissues, earthworm tissues, and soil solutions. A separate treatment with agricultural lime was also conducted for comparison to evaluate whether any observed improvements were attributable to the liming capacity of the WTRs. After completion of the trials, all samples were subjected to a wet-dry cycle, and the experiments were repeated (i.e., simulating longer-term effects in the field). Both types of WTRs significantly increased the biomass of plants, and in some treatments, survival of earthworms was also enhanced compared to nonamended soils. Excess plant tissue element concentrations and element concentrations in soil solutions were reduced in amended soils. The implications are that adding WTRs to mining-impacted soils is a potentially viable, sustainable, and low-cost remediation method that could be used globally to improve the soil condition. Environ Toxicol Chem 2020;39:1277-1291. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC., (© 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.)

Effective environmental assessment and management requires quantifiable biodiversity targets. Biodiversity benchmarks define these targets by focusing on specific biodiversity metrics, such as species richness. However, setting fixed targets can be challenging because many biodiversity metrics are highly variable, both spatially and temporally. We present a multivariate, hierarchical Bayesian method to estimate biodiversity benchmarks based on the species richness and cover of native terrestrial vegetation growth forms. This approach uses existing data to quantify the empirical distributions of species richness and cover within growth forms, and we use the upper quantiles of these distributions to estimate contemporary, "best-on-offer" biodiversity benchmarks. Importantly, we allow benchmarks to differ among vegetation types, regions, and seasons, and with changes in recent rainfall. We apply our method to data collected over 30 yr at ~35,000 floristic plots in southeastern Australia. Our estimated benchmarks were broadly consistent with existing expert-elicited benchmarks, available for a small subset of vegetation types. However, in comparison with expert-elicited benchmarks, our data-driven approach is transparent, repeatable, and updatable; accommodates important spatial and temporal variation; aligns modeled benchmarks directly with field data and the concept of best-on-offer benchmarks; and, where many benchmarks are required, is likely to be more efficient. Our approach is general and could be used broadly to estimate biodiversity targets from existing data in highly variable environments, which is especially relevant given rapid changes in global environmental conditions., (© 2019 The Authors. Ecological Applications published by Wiley Periodicals, Inc. on behalf of Ecological Society of America.)

Biodiversity offsetting typically involves the trade of certain losses of habitat with uncertain future conservation benefits. Predicting the latter requires estimates of two outcomes; the biodiversity losses without conservation management (averted loss), and the biodiversity gains with conservation management (management gain). However, because empirical data to inform these estimates are limited, they are normally guided by expert opinion, often derived via unstructured methods without consideration of uncertainty. Here we used a structured elicitation with 29 experts to gather estimates of averted loss and management gain at offset sites. We used two methods; (i) experts estimated change in an aggregate biodiversity value (vegetation condition) and; (ii) experts provided probabilistic estimates of change for individual vegetation condition attributes, such as the richness and cover of plant growth forms. On average, experts predicted there would be only modest improvements with conservation management, yet uncertainty and variation among experts was large; in some cases, conservation benefits were not predicted. Estimates of change in vegetation condition suggested that benefits were from both averted loss and management gains and were thought to most likely arise in cases where starting condition was low to moderate. Similar patterns were observed for individual vegetation condition attributes, with management gains, relative to a reference, tending to be negatively correlated with starting value. Our study finds that: (i) on average, gains at offset sites are expected to be small, (ii) at many sites, experts do not believe gains can be obtained, and (iii) experts' opinions can be divergent resulting in elevated levels of uncertainty. The potential for losses under conservation management highlights the need to: identify those components of biodiversity most likely to benefit from conservation management; better understand those situations when offset obligations are most likely to be met and conversely those situations with higher risk; and further develop offset mechanisms that encourage early or prior gains. These findings together with the global proliferation of biodiversity offsetting, provide a strong imperative to improve empirical data and investment in long-term, site-based monitoring of biodiversity outcomes at offset sites., Competing Interests: The authors have declared that no competing interests exist.

Understanding the physiological tolerances of ectotherms, such as thermal limits, is important in predicting biotic responses to climate change. However, it is even more important to examine these impacts alongside those from other landscape changes: such as the reduction of native vegetation cover, landscape fragmentation and changes in land use intensity (LUI). Here, we integrate the observed thermal limits of the dominant and ubiquitous meat ant Iridomyrmex purpureus across climate (aridity), land cover and land use gradients spanning 270 km in length and 840 m in altitude across northern New South Wales, Australia. Meat ants were chosen for study as they are ecosystem engineers and changes in their populations may result in a cascade of changes in the populations of other species. When we assessed critical thermal maximum temperatures (CT max ) of meat ants in relation to the environmental gradients we found little influence of climate (aridity) but that CT max decreased as LUI increased. We found no overall correlation between CT max and CT min . We did however find that tolerance to warming was lower for ants sampled from more arid locations. Our findings suggest that as LUI and aridification increase, the physiological resilience of I. purpureus will decline. A reduction in physiological resilience may lead to a reduction in the ecosystem service provision that these populations provide throughout their distribution., Competing Interests: Nigel R. Andrew is an Academic Editor for PeerJ.

Drinking water treatment residuals (WTRs), the by-product of water clarification processes, are routinely disposed of via landfill however there is a growing body of research that demonstrates the material has great potential for beneficial use in environmental applications. Application to agricultural land is one option showing great promise (i.e. a low cost disposal route that provides organic matter input to soils and other potential benefits), however questions remain as to the impact such applications may have on earthworm survival and behaviour and also on the potential effects it may have on soil porewater chemistry. This study examined the leachability of elements within two types of WTRs (one Al- and one Fe- based) from England via 0.001 M CaCl 2 solution, at varying pH, and via the Community Bureau of Reference (BCR) sequential extraction scheme. Earthworm avoidance, survival, growth, reproduction and element concentrations were examined in WTR-amended sandy soils (0%, 5%, 10%, 20% w/w), while soil porewaters were also recovered from experimental units and examined for element concentrations. The results revealed leachable element concentrations to be very low in both types of WTRs tested and so element leaching from these WTRs would be unlikely to pose any threat to ecosystems under typical agricultural soil conditions. However, when the pH was lowered to 4.4 there was a substantial release of Al from the Al-WTRs (382 mg/kg). Soil porewater element concentrations were influenced to some degree by WTR addition, warranting further examination in terms of any potential implications for nutrient supply or limitation. Earthworm avoidance of WTR-amended soil was only observed for Al-WTRs and only at the maximum applied rate (20% w/w), while survival of earthworms was not affected by either WTR type at any application rate. Earthworm growth and reproduction (cocoon production) were not affected at a statistically significant level but this needs further examination over a longer period of exposure. Increased assimilation of Al and Fe into earthworm tissues was observed at some WTR application rates (maximum fresh weight concentrations of 42 mg/kg for Al and 167 mg/kg for Fe), but these were not at levels likely to pose environmental concerns., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The role of climatic legacies in regulating community assembly of above- and belowground species in terrestrial ecosystems remains largely unexplored and poorly understood. Here, we report on two separate regional and continental empirical studies, including >500 locations, aiming to identify the relative importance of climatic legacies (climatic anomaly over the last 20,000 years) compared to current climates in predicting the relative abundance of ecological clusters formed by species strongly co-occurring within two independent above- and belowground networks. Climatic legacies explained a significant portion of the variation in the current community assembly of terrestrial ecosystems (up to 15.4%) that could not be accounted for by current climate, soil properties, and management. Changes in the relative abundance of ecological clusters linked to climatic legacies (e.g., past temperature) showed the potential to indirectly alter other clusters, suggesting cascading effects. Our work illustrates the role of climatic legacies in regulating ecosystem community assembly and provides further insights into possible winner and loser community assemblies under global change scenarios., (© 2018 John Wiley & Sons Ltd.)

Cadmium (Cd) contaminated soils from the Mae Sot district in northwest Thailand, a region in which rice Cd concentrations often exceed health limits (0.4 mg/kg) set by the World Health Organisation, were examined for isotopically exchangeable Cd (Cd E values using a 111 Cd spike) to determine how this rates as a predictor of rice grain Cd in comparison with soil total Cd and solution extractable Cd (using the commonly applied BCR scheme and, in an attempt to distinguish carbonate bound forms, the Tessier soil sequential extraction scheme reagents). Step 1 of the BCR scheme (0.11 M CH 3 COOH) and step 1 of the Tessier scheme (1M MgCl 2 ) showed the highest R 2 values in regressions with rice Cd (91% and 90%, respectively), but all predictors were strongly linked to rice Cd (p < 0.001) and could be used for prediction purposes. One soil, of the six tested, was an exception to this, where all predictors over-estimated grain Cd by a factor of 2.5-5.7, suggesting that rice grain Cd had been restricted here by the differing flooding regime and subsequent changes to redox conditions. E values and Tessier step 1 extractions were closely related, indicating that these measurements access similar pools of soil Cd. Separately, the isotopic exchangeability (representing bioavailability) of Cd was also assessed in two soils amended with rice husk and miscanthus biochars (0, 1, 5, 10, 15 and 20% w/w) in order to assess the utility of the biochars as a soil amendment for immobilising Cd in situ. One soil showed significant reductions in Cd E value at 5% rice husk biochar addition and at 15% miscanthus biochar addition however, based on the E value-rice grain Cd regression relationship previously established, the E values in the amended soils still predicted for a rice Cd concentration above the health limit. In the second soil, neither of the biochars successfully reduced the Cd E value. This indicates that further work is needed to customise biochar properties to suit specific soil and contaminant situations if they are to be used successfully for remediation of metal contaminated soils., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Scientists have largely neglected the effects of grazing on soil microbial communities despite their importance as drivers of ecosystem functions and services. We hypothesized that changes in soil properties resulting from grazing regulate the diversity of soil microbes by releasing/suppressing subordinate microbial taxa via competition. To test this, we examined how intensity of vertebrate herbivores influences the diversity and composition of soil bacteria and fungi at 216 soil samples from 54 sites across four microsites. Increasing grazing intensity reduced soil carbon, suppressing the dominant bacterial phylum Actinobacteria (indirectly promoting bacterial diversity) and increasing the dominant fungal phylum Ascomycetes (indirectly reducing fungal diversity). Our data provide novel evidence that grazing modulates the diversity and composition of soil microbes via increases or reductions in competition by dominant taxa. Our results suggest that grazing can potentially alter soil function by altering microbial community composition, providing a clear link between grazing management, carbon availability and ecosystem functions., (© 2017 by the Ecological Society of America.)

Recruitment of the European eel (Anguilla anguilla) has fallen steadily in recent decades, with current levels understood to be at around 5% of those in the 1970s, and the species is now widely recognised as being endangered. Changes in ocean currents, climate shifts, habitat loss, overfishing, barriers to migration, increased predation, plastic litter and exposure to chemicals have all been postulated as potential causative factors. Several studies have shown a general decline in eel quality (lower lipid content and body condition) over time that may be linked to reduced reproductive success. In this study, data from an eel sampling campaign in 1987 are compared with recent data (2004-2008) for eels in Scotland to assess any temporal changes in eel quality indicators and also to assess any links between current levels of chemical exposure and eel quality. Mean lipid levels, as a percentage of wet muscle mass, were higher in 2004-2008 (37 ± 1.9% SE) than in 1986 (21 ± 0.9% SE). By contrast, mean body condition index (K) was slightly lower in the latter period. Considering the 2004-2008 samples, significant inter-site variation was observed for condition index K, while intra-site variation was observed for lipid content and physical parameters relative to age (i.e. mass/age, length/age and lipid/age ratios); however, the variations observed could not be linked to differences in chemical body burdens, indicating that no chemical impacts on the parameters assessed are discernible during the continental life stage of eels in Scotland.

Under the Water Framework Directive (WFD) lakes are classified according to a variety of criteria. This classification facilitates state of the environment assessments and helps identify work needed to achieve the objectives of the WFD, which are broadly to maintain and/or restore water quality and ecological status at a level recognised as good or high. To achieve high or good status, lakes must meet a criterion for total phosphorus (TP) that is linked to a predicted reference condition value that is derived by various models. Lakes which fail to meet good status may require expensive remedial actions to be undertaken, thus accurate identification of the reference condition TP concentration is vital for effective environmental management. However, the models currently employed could be improved for some regions, particularly those with carbon rich soils. By examining 19 reference condition lakes (i.e. lakes essentially non-impacted by humans) in peaty areas of Scotland, we found that a simple parameter linked to water colour and humic substances was a better predictor of TP than the currently employed models (R(2) 0.585 vs R(2) < 0.01). Therefore, for Scotland and elsewhere, in regions with carbon rich soils and lakes with humic waters the TP predictive models could be improved by development and incorporation of a parameter related to water colour and humic components., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The Mae Tao watershed, northwest Thailand, has become contaminated with cadmium (Cd) as a result of zinc ore extraction (Padaeng deposit) in the nearby Thanon-Thongchai mountains. Consumption of contaminated rice has led to documented human health impacts. The aim of this study was to elucidate transfer pathways from creek and canal waters to the paddy field soils near Baan Mae Tao Mai village and to determine the relationship between Cd speciation in the soil and uptake by rice plants. Transfer mainly occurred in association with particulate matter during flooding and channel dredging and, in contrast with many other studies, most of the soil Cd was associated with exchangeable and carbonate-bound fractions. Moreover, there was a linear relationship between soil total Cd and rice grain Cd (R(2) = 0.715), but a stronger relationship between both the Tessier-exchangeable soil Cd and the BCR-exchangeable soil Cd and rice grain Cd (R(2) = 0.898 and 0.862, respectively)., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Although aging processes are important in risk assessment for metals in soils, the aging of Ni added to soils has not been studied in detail. In this study, after addition of water soluble Ni to soils, the changes over time in isotopic exchangeability, total concentrations and free Ni(2+) activity in soil pore water, were investigated in 16 European soils incubated outdoors for 18 months. The results showed that after Ni addition, concentrations of Ni in soil pore water and isotopic exchangeability of Ni in soils initially decreased rapidly. This phase was followed by further decreases in the parameters measured but these occurred at slower rates. Increasing soil pH increased the rate and extent of aging reactions. Semi-mechanistic models, based on Ni precipitation/nucleation on soil surfaces and micropore diffusion, were developed and calibrated. The initial fast processes, which were attributed to precipitation/nucleation, occurred over a short time (e.g. 1h), afterwards the slow processes were most likely controlled by micropore diffusion processes. The models were validated by comparing predicted and measured Ni aging in three additional, widely differing soils aged outdoors for periods up to 15 months in different conditions. These models could be used to scale ecotoxicological data generated in short-term studies to longer aging times., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

We investigated the feasibility of coupling passive sampling and in vitro bioassay techniques for both chemical and ecotoxicological assessment of complex mixtures of organic contaminants in water. Silicone rubber passive sampling devices (SR-PSDs) were deployed for 8-9 weeks in four streams and an estuary of an agricultural catchment in North East (NE) Scotland. Extracts from the SR-PSDs were analysed for freely dissolved hydrophobic organic contaminants (HOCs) and screened for wide range of pesticides. The total concentrations of dissolved PAHs (∑PAH(40), parent and branched) in the water column of the catchment varied from 38 to 69 ng L(-1), whilst PCBs (∑PCB(32)) ranged 0.02-0.06 ng L(-1). A number and level of pesticides and acid/urea herbicides of varying hydrophobicity (logK(OW)s ~2.25 to ~5.31) were also detected in the SR extracts, indicating their occurrence in the catchment. The acute toxicity and EROD induction potentials of SR extracts from the study sites were evaluated with rainbow trout liver (Oncorhynchus mykiss; RTL-W1) cell line. Acute cytotoxicity was not observed in cells following 48 h exposure to the SR extracts using neutral red uptake assay as endpoint. But, on a sublethal level, for every site, statistically significant EROD activity was observed to some degree following 72 h exposure to extracts, indicating the presence of compounds with dioxin-like effect that are bioavailable to aquatic organisms in the water bodies of the catchment. Importantly, only a small fraction of the EROD induction could be attributed to the PAHs and PCBs that were determined. This preliminary study demonstrates that the coupling of silicone rubber passive sampling techniques with in vitro bioassays is feasible and offers a cost effective early warning signal on water quality deterioration., (Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.)

Uranium associations with colloidal and truly dissolved soil porewater components from two Ministry of Defence Firing Ranges in the UK were investigated. Porewater samples from 2-cm depth intervals for three soil cores from each of the Dundrennan and Eskmeals ranges were fractionated using centrifugal ultrafiltration (UF) and gel electrophoresis (GE). Soil porewaters from a transect running downslope from the Dundrennan firing area towards a stream (Dunrod Burn) were examined similarly. Uranium concentrations and isotopic composition were determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Multi-Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS), respectively. The soils at Dundrennan were Fe- and Al-rich clay-loam soils whilst at Eskmeals, they were Fe- and Al-poor sandy soils; both, however, had similar organic matter contents due to the presence of a near-surface peaty layer at Eskmeals. These compositional features influenced the porewater composition and indeed the associations of U (and DU). In general, at Dundrennan, U was split between large (100kDa-0.2μm) and small (3-30kDa) organic colloids whilst at Eskmeals, U was mainly in the small colloidal and truly dissolved fractions. Especially below 10cm depth, association with large Fe/Al/organic colloids was considered to be a precursor to the removal of U from the Dundrennan porewaters to the solid phase. In contrast, the association of U with small organic colloids was largely responsible for inhibiting attenuation in the Eskmeals soils. Lateral migration of U (and DU) through near-surface Dundrennan soils will involve both large and small colloids but, at depth, transport of the smaller amounts of U remaining in the porewaters may involve large colloids only. For one of the Dundrennan cores the importance of redox-related processes for the re-mobilisation of DU was also indicated as Mn(IV) reduction resulted in the release of both Mn(II) and U(VI) into the truly dissolved phase., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Water treatment residuals (WTRs) are the by-products of drinking water clarification processes, whereby chemical flocculants such as alum or ferric chloride are added to raw water to remove suspended clay particles, organic matter and other materials and impurities. Previous studies have identified a strong phosphorus (P) fixing capacity of WTRs which has led to experimentation with their use as P-sorbing materials for controlling P discharges from agricultural and forestry land. However, the P-fixing capacity of WTRs and its capacity to retain sorbed P under anaerobic conditions have yet to be fully demonstrated, which is an issue that must be addressed for WTR field applications. This study therefore examined the capacity of WTRs to retain sorbed P and sorb further additional P from aqueous solution under both aerobic and anaerobic conditions. An innovative, low cost apparatus was constructed and successfully used to rapidly establish anoxic conditions in anaerobic treatments. The results showed that even in treatments with initial solution P concentrations set at 100 mg l(-1), soluble reactive P concentrations rapidly fell to negligible levels (due to sorption by WTRs), while total P (i.e. dissolved + particulate and colloidal P) was less than 3 mg l(-1). This equated to an added P retention rate of >98% regardless of anaerobic or aerobic status, indicating that WTRs are able to sorb and retain P in both aerobic and anaerobic conditions., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (alpha, beta, gamma-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban approximately 30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. alpha-HCH, beta-HCH and HCB concentrations were very low (generally <3 microg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p'-DDE concentrations. More drastic reductions were evident for gamma-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

The mobility and bioavailability of depleted uranium (DU) in soils at a UK Ministry of Defence (UK MoD) weapons testing range were investigated. Soil and vegetation were collected near a test-firing position and at eight points along a transect line extending approximately 200 m down-slope, perpendicular to the firing line, toward a small stream. Earthworms and porewaters were subsequently separated from the soils and both total filtered porewater (<0.2 microm) and discrete size fractions (0.2 microm-100 kDa, 100-30 kDa, 30-3 kDa, and <3 kDa)obtainedvia centrifugal ultrafiltration were examined. Uranium concentrations were determined by inductively coupled plasma optical emission spectrometry (ICP-OES) for soils and ICP-mass spectrometry (MS) for earthworms and porewaters, while 235U:238U atom ratios were determined by multicollector (MC)-ICP-MS. Comparison of the porewater and earthworm isotopic values with those of the soil solids indicated that DU released into the environment during weapons test-firing operations was more labile and more bioavailable than naturally occurring U in the soils at the testing range. Importantly, DU was shown to be present in soil porewater even at a distance of approximately 185 m from the test-firing position and, along the extent of the transect was apparently associated with organic colloids.

Methods for the fractionation of aquatic colloids require careful application to ensure efficient, accurate and reproducible separations. This paper describes the novel combination of mild colloidal fractionation and characterisation methods, namely centrifugal ultrafiltration, gel electrophoresis and gel filtration along with spectroscopic (UV-visible) and elemental (Inductively Coupled Plasma-Optical Emission Spectroscopy, Inductively Coupled Plasma-Mass Spectrometry) analysis, an approach which produced highly consistent results, providing improved confidence in these methods. Application to the study of the colloidal and dissolved components of soil porewaters from one soil at a depleted uranium (DU)-contaminated site revealed uranium (U) associations with both large (100 kDa-0.2 microm) and small (3-30 kDa) humic colloids. For a nearby soil with lower organic matter content, however, association with large (100 kDa-0.2 microm) iron (Fe)-aluminium (Al) colloids in addition to an association with small (3-30 kDa) humic colloids was observed. The integrated colloid fractionation approach presented herein can now be applied with confidence to investigate U and indeed other trace metal migration in soil and aquatic systems.

Depleted uranium (DU) has become a soil contaminant of considerable concern in many combat zones and weapons-testing sites around the world, including locations in Europe, the Middle East and the USA, arising from its dispersion via the application of DU-bearing munitions. Once DU is released into the environment its mobility and bioavailability will, like that of other contaminants, largely depend on the type of associations it forms in soil and on the nature of the soil components to which it binds. In this study we used the BCR sequential extraction scheme to determine the partitioning of DU amongst soil fractions of texturally varying soils from locations affected by weapons-testing activities. Isotopic analyses (MC-ICP-MS and alpha-spectrometry) were performed to verify the presence of DU in whole soils and soil fractions and to determine any preferential partitioning of the contaminant. Results identified soil organic matter as being consistently the most important component in terms of DU retention, accounting for 30-100% of DU observed in the soils examined. However, at greater distances from known contamination points, DU was also found to be largely associated with the exchangeable fraction, suggesting that DU can be mobilised and transported by surface and near-surface water and does remain in an exchangeable (and thus potentially bioavailable) form in soils.

Depleted uranium (DU) weapons testing programmes have been conducted at two locations within the UK. An investigation was therefore carried out to assess the extent of any environmental contamination arising from these test programmes using both alpha spectrometry and mass spectrometry techniques. Uranium isotopic signatures indicative of DU contamination were observed in soil, plant and earthworm samples collected in the immediate vicinity of test firing points and targets, but contamination was found to be localised to these areas. This paper demonstrates the superiority of the (235)U : (238)U ratio over the (234)U : (238)U ratio for identifying and quantifying DU contamination in environmental samples, and also describes the respective circumstances under which alpha spectrometry or mass spectrometry may be the more appropriate analytical tool.

Aging refers to the processes by which the mobility and bioavailability/toxicity of metals added to soil decline with time. Although long-term aging is a key process that needs to be considered in the risk assessment of metals in field soils, the long-term aging of Cu added to soils has not been studied in detail. In this study, the effects of aging on Cu isotopic exchangeability, total Cu in soil pore water, pore water free Cu2+ activity, and "available" Cu measured by the technique of diffusive gradient in thin film (DGT-Cu) were investigated in 19 European soils at two total Cu concentrations shown to inhibit plant (tomato) growth by 10 and 90%. After addition of Cu, the soils were leached, incubated outdoors, and sampled regularly over a 2-year period. The results showed that when water soluble Cu was added to soils, concentrations of Cu determined by each of the techniques tended to decrease rapidly initially, followed by further decreases at slow rates. Soil pH was a vital factor affecting the aging rate of Cu added to soils. The relatively low solubility products and low isotopic exchangeabilities of Cu in calcareous soils immediately after addition of soluble Cu2+ suggested Cu2+ probably precipitated in these soils as Cu2(OH)2CO3 (malachite) and Cu(OH)2. Isotopic dilution was found to be a robust technique for measuring rates of long-term aging reactions. A semi-mechanistic model was developed to describe the rate and extent of Cu aging across soils as affected by soil pH and other physicochemical parameters. Although not measured directly, it is inferred from soil physicochemical controls on Cu aging that processes of precipitation/nucleation of Cu in soils and hydrolysis of Cu2+ followed by a diffusion process controlled the decrease in Cu availability with time. The model was validated by testing it against field soils with different contamination histories and was found to successfully predict the isotopic exchangeability of Cu added to soils based on two parameters: soil pH and time.

Isotopic techniques have become a valuable tool for assessing the lability or potential availability of elements in soil. Until now, work on soil Cu has been limited to E-value methods where soil solution extracts are obtained by physical means due to the very short (12.4 h) half-life of the radio isotope 64Cu. However, a stable isotope method has recently been developed for determining soil Cu E values that utilizes enhancement of the 65Cu isotope in soil and measurement of the subsequent ratio with 63Cu. We have developed an L-value technique for soil Cu, where plants are used to sample the soil solution and therefore give a direct measure of the plant available Cu. The L-value technique developed was then compared, and found to be equivalent, with E values using equilibration periods up to and including the growth period of plants in the L-value method.

Patterns in the spatial distribution of organisms provide important information about mechanisms that regulate the diversity of life and the complexity of ecosystems. Although microorganisms may comprise much of the Earth's biodiversity and have critical roles in biogeochemistry and ecosystem functioning, little is known about their spatial diversification. Here we present quantitative estimates of microbial community turnover at local and regional scales using the largest spatially explicit microbial diversity data set available (> 10(6) sample pairs). Turnover rates were small across large geographical distances, of similar magnitude when measured within distinct habitats, and did not increase going from one vegetation type to another. The taxa-area relationship of these terrestrial microbial eukaryotes was relatively flat (slope z = 0.074) and consistent with those reported in aquatic habitats. This suggests that despite high local diversity, microorganisms may have only moderate regional diversity. We show how turnover patterns can be used to project taxa-area relationships up to whole continents. Taxa dissimilarities across continents and between them would strengthen these projections. Such data do not yet exist, but would be feasible to collect.

The effects of soil properties and zinc (Zn) availability on the toxicity of Zn to soil microbial processes are poorly understood. Three soil microbial processes--potential nitrification rate (PNR), substrate (glucose)-induced respiration (SIR), and a maize residue respiration (MRR)--were measured in 15 European topsoils (pH 3.0-7.5; total Zn 7-191 mg/kg) that were freshly spiked with ZnCl2. The Zn toxicity thresholds of 20 to 50% effective concentrations (EC20s and EC50s) based on total concentrations of Zn in soil varied between 5- and 26-fold among soils, depending on the assay. The Zn toxicity thresholds based on Zn concentrations in soil solution varied at least 10-fold more than corresponding total metal thresholds. Soil pH had no significant effect on soil total Zn toxicity thresholds, whereas significant positive correlations were found between these thresholds and background Zn for the PNR and SIR test (r = 0.74 and 0.71, respectively; log-log correlations). No such trend was found for the MRR test. Soil solution-based thresholds showed highly significant negative correlations with soil pH for all assays that might be explained by competition of H+ for binding sites, as demonstrated for aquatic species. The microbial assays were also applied to soils collected under galvanized pylons (three sites) where concentrations of total Zn were up to 2,100 to 3,700 mg Zn/kg. Correlations between concentrations of total Zn and microbial responses were insignificant at all sites even though spiking reference samples to equivalent concentrations reduced microbial activities up to more than 10-fold. Differences in response between spiked and field soils are partly but not completely attributed to the large differences in concentrations of Zn in soil solution. We conclude that soil pH has no significant effect on Zn toxicity to soil microbial processes in laboratory-spiked soils, and we suggest that community tolerance takes place at both background and elevated Zn concentrations in soil.

Six sewage sludges from five sewage treatment plants in Australia were incubated for up to 21 months. Carbon losses at the end of the 21-mo incubation varied substantially. The remaining organic matter was isolated by treatment with hydrofluoric acid (HF) and characterized using a range of solid-state (13)C nuclear magnetic resonance (NMR) spectroscopic techniques. By every measure (signal distribution in cross polarization [CP] and Bloch decay [BD] spectra, carbon NMR observability determined by spin counting, and the appearance of proton spin relaxation editing subspectra), the chemical composition of the residual organic matter appeared to be little different from that of the original sludges, even for those sludges that experienced the greatest carbon losses. Importantly, these NMR properties distinguish sewage sludge organic matter from soil organic matter. Thus, it should be possible to follow the decomposition of sewage sludge organic matter applied to soils in the field using solid-state (13)C NMR spectroscopy.

The technique of diffusive gradients in thin films (DGT) has been suggested to sample an available fraction of metals in soil. The objectives of this study were to compare DGT measurements with commonly measured fractions of Zn in soil, viz, the soil solution concentration and the total Zn concentration. The DGT technique was used to measure fluxes and interfacial concentrations of Zn in three series of field-contaminated soils collected in transects toward galvanized electricity pylons and in 15 soils amended with ZnCl2 at six rates. The ratio of DGT-measured concentration to pore water concentration of Zn, R, varied between 0.02 and 1.52 (mean 0.29). This ratio decreased with decreasing distribution coefficient, Kd, of Zn in the soil, which is in agreement with the predictions of the DGT-induced fluxes in soils (DIFS) model. The R values predicted with the DIFS model were generally larger than the observed values in the ZnCl2-amended soils at the higher Zn rates. A modification of the DIFS model indicated that saturation of the resin gel was approached in these soils, despite the short deployment times used (2 h). The saturation of the resin with Zn did not occur in the control soils (no Zn salt added) or the field-contaminated soils. Pore water concentration of Zn in these soils was predicted from the DGT-measured concentration and the total Zn content. Predicted values and observations were generally in good agreement. The pore water concentration was more than 5 times underpredicted for the most acid soil (pH = 3) and for six other soils, for which the underprediction was attributed to the presence of colloidal Zn in the soil solution.

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.

Six sewage sludges from five sewage treatment plants in Australia were characterized using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Spectra were acquired both before and after removal of mineral components through treatment with hydrofluoric acid (HF). Carbon mass balance indicated that little organic matter was lost on HF treatment, which significantly improved NMR sensitivity and spectral resolution, and decreased acquisition time and hence cost of NMR analysis. Two NMR techniques were used, the standard cross polarization (CP) technique and Bloch decay (BD). The BD technique had not been applied previously to the analysis of sewage sludge. For each sludge sample, both before and after HF treatment, the BD spectrum contained significantly more alkyl carbon. Spin counting, another technique applied to sewage sludge here for the first time, showed that the BD spectra of the HF-treated sludges were quantitative, while approximately 30% of the CP NMR signal went undetected. The discrepancy between CP and BD spectra was attributed to the presence of alkyl carbon with such high molecular mobility that the efficiency of cross polarization is affected. This study shows that sewage sludge organic matter is significantly different in chemistry to soil organic matter and has implications for the application of sewage sludge to agricultural land.