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In recent years, many community-based conservancies (CBCs) led by non-governmental organizations (NGOs) have been established on land inhabited by pastoralists in Northern Kenya. Despite a growing body of research, little attention has been paid to the impacts on pastoralists’ climate change adaptation. We provide a deeper understanding by considering NGO-led community-based conservation (NGO-led CBC) as a new frontier of territorialization and adaptation to climate change and variability as a social-natural process. Based on an analysis of primary data collected in Samburu County, Kenya, we show that NGO-led CBC involves resource enclosures that aggravate conflicts over land rights and pastoralists’ vulnerability to climate change and variability by constraining their mobility. In relation, the legal and institutional environment promoted by NGO-led CBC leads to increased control over ecologically vibrant lands, which erodes pastoralists’ land tenure security and climate change adaptation. Although NGO-led CBC plays an important role in enhancing access to external finance and incentivizing diversification, governance mechanisms remain opaque and overshadow local institutions. Overall, we highlight the need for actors to carefully consider the implications of this conservation/development model for already hard-pressed land-dependent communities.

BackgroundEffective management of the COVID-19 pandemic required rapid expansion of diagnosis. The introduction of antigen tests presented an opportunity to decentralize testing, but raised challenges with ensuring accurate and timely reporting of testing data, which is essential to guide the response. Digital solutions can help address this challenge and provide more efficient means of monitoring and quality assurance.MethodsUganda’s existing laboratory investigation form was digitized in the form of an Android-based application, eLIF, which was developed by the Central Public Health Laboratory and implemented in 11 high-volume facilities between December 2021 and May 2022. The app enabled healthcare workers to report testing data via mobile phone or tablet. Uptake of the tool was monitored through a dashboard that enabled real-time visibility into data being transmitted from sites, as well as qualitative insights from site visits and online questionnaires.Results and discussionA total of 15,351 tests were conducted at the 11 health facilities during the study period. Of these, 65% were reported through eLIF, while 12% were reported through preexisting Excel-based tools. However, 23% of tests were only captured in paper registers and not transmitted to the national database, illustrating the need for increased uptake of digital tools to ensure real-time data reporting. While data captured through eLIF were transmitted to the national database within 0–3 days (min, max), data transmitted through Excel were transmitted in within 0–37 days (min, max), and data for paper-based reporting took up to 3 months. The majority of healthcare workers interviewed in an endpoint questionnaire responded that eLIF improved timeliness of patient management, and reduced reporting time. However, some functions of the app were not successfully implemented, such as providing random selections of samples for external quality assurance and enabling seamless linkage of these data. Challenges arose from broader operational complexities, such as staff workload, frequent task-shifting and unexpected changes to facility workflows, which limited adherence to the envisioned study procedures. Ongoing improvements are needed to adjust to these realities, to strengthen the technology and support to healthcare workers using it, to optimize the impact of this digital intervention.

IntroductionPerfusion imaging strongly predicts coronary artery disease (CAD), whereas cardiac volumes and left ventricular ejection fraction (LVEF) strongly predict mortality. Compared to conventional Anger single-photon emission computed tomography (SPECT) cameras, cadmium-zinc-telluride (CZT) cameras provide higher resolution, resulting in different left ventricular volumes. The cadmium-zinc-telluride D-SPECT camera is commonly used to image in the upright position, which introduces changes in left ventricular loading conditions and potentially alters left ventricular volumes. However, little or no data exist on the predictive value of left ventricular volumes and ejection fraction when acquired in the upright position. We investigated models for the prediction of CAD and mortality, comparing upright and supine imaging.MethodsA retrospective study of patients with upright/supine stress and rest imaging and coronary angiography within 3 months was performed. Univariate and multivariable analyses were performed to predict abnormal angiograms and all-cause mortality.ResultsOf the 392 patients, 210 (53.6%) had significant angiographic CAD; 78 (19.9%) patients died over 75 months. The best multivariable model for CAD included the supine summed stress score and supine stress LVEF, with an area under the receiver operating characteristic of 0.862, a sensitivity of 76.7%, and a specificity of 82.4%, but this model was not statistically superior to the best upright model. The best multivariable models for mortality included age, diabetes, history of cardiovascular disease, and end-systolic volume, with the upright and supine models being equivalent.DiscussionAngiographic CAD was best predicted by the supine summed stress score and LVEF but was not statistically superior to the next-best upright model. Mortality was best predicted by end-systolic volume in combination with age, diabetes status, and cardiovascular disease status, with equivalent results from the upright and supine images.

In today’s evolving cybersecurity landscape, distributed denial-of-service (DDoS) attacks have become one of the most prolific and costly threats. Their capability to incapacitate network services while causing millions of dollars in damages has made effective DDoS detection and prevention imperative for businesses and government entities alike. Prior research has found shallow and deep learning classifiers to be invaluable in detecting DDoS attacks; however, there is an absence of research concerning time-based features and classification among many DDoS attack types. In this article, we propose and study the efficacy of 25 time-based features to detect and classify 12 types of DDoS attacks using binary and multiclass classification. Furthermore, we ran experiments to compare the performance of eight traditional machine learning classifiers and one deep learning classifier using two different scenarios. Our findings show that the majority of models provided ~99% accuracy on both the control and time-based experiments in detecting DDoS attacks while yielding ~70% accuracy in classifying specific DDoS attack types. Training on the proposed time-based feature subset was found to be effective at reducing training time without compromising test accuracy; thus, the smaller time-based feature subset alone is beneficial for near-real time applications that incorporate continuous learning.

Grinding aids (GAs) are polar chemicals introduced in cement mills in either liquid or powder form to improve on mill grindability efficiency. Studies have shown that some GAs not only help in grinding efficiency but also play vital roles in improving the product particle size distribution, product ability to flow in the mill, grinding energy reduction, and improvement on the separator efficiency. This review investigated the impacts of the GAs on the performance of some properties of cement when used as either mortar and/or concrete. The influence of the GAs incorporation in cement grinding on properties such as workability and setting times of the placed concrete and/or mortar has been covered in this review. The performance of GAs on ordinary portland cement (OPC) and blended cements with other supplementary cementitious materials such as pozzolana, fly ash, and slag has also been discussed. This is in view to tapping the maximum benefits of using GAs in cement production and use. This review work established that GAs have a positive influence on mill performance when properly applied. It further established that blended cements work better when dosed with additives such as GAs and/or quality improvers when compared to OPC. The review work demonstrated that some superplasticizers help in lowering the water demand in highly blended pozzolanic-based cements. The review finally recommended that the future course of action in the production of blended cements should apply GAs. This is in order to help produce highly replaced blended cements that are sustainable.

The Domain Name System (DNS) is among the most ubiquitous and important protocols for network communication; however, security concerns regarding DNS have been on the rise and demand for encrypted traffic has followed suit. Using a publicly available dataset, this work compares 10 different machine learning classifiers using stratified 10-fold cross-validation. The classifiers are used to determine the most effective and efficient way of detecting malicious DNS over Hypertext Transfer Protocol Secure (HTTPS) traffic, dubbed DoH traffic. Model performance is evaluated on Non-DoH vs. DoH traffic, then tested on benign vs. malicious DoH traffic. Additionally, this paper seeks to build upon existing research by removing noise and introducing feature selection methods and feature explainability to produce a better model for real-world deployment. After eliminating five overfitting features, our findings indicate that light gradient boosting machine (LGBM) yielded the highest accuracy to training time ratio while approaching 0% error using 20 top features.

Background Asymptomatic and pre-symptomatic SARS-CoV-2 infections may contribute to ongoing community transmission, however, the benefit of routine screening of asymptomatic individuals in low-risk populations is unclear. Methods To identify SARS-CoV-2 infections 553 seronegative individuals were prospectively followed for 52 weeks. From 4/2020-7/2021, participants submitted weekly self-collected nasal swabs for rtPCR and completed symptom and exposure surveys. Results Incident SARS2-CoV-2 infections were identified in 9/553 (1.6%) participants. Comparisons of SARS2-CoV-2(+) to SARS2-CoV-2(-) participants revealed significantly more close contacts outside the household (median: 5 versus 3; p = 0.005). The incidence of infection was higher among unvaccinated/partially vaccinated than among fully vaccinated participants (9/7,679 versus 0/6,845 person-weeks; p = 0.004). At notification of positive test result, eight cases were symptomatic and one pre-symptomatic. Conclusions These data suggest that weekly SARS2-CoV2 surveillance by rtPCR did not efficiently detect pre-symptomatic infections in unvaccinated participants.

This paper reports study findings on the use of Lysinibacillus sphaericus (at 1.0 × 107 cells/ml concentration) to enhance and improve the physicomechanical and chemical properties of blended Ordinary Portland Cement (OPC). Blending was done separately with pulverized fly ash (PFA) and natural pozzolana (volcanic tuff) at substitution levels of 10%, 20%, 30%, 40%, 50%, 60%, and 70%. Mortar prisms of dimensions 40 mm by 40 mm by 160 mm were prepared and cured for the 2nd, 7th, 28th, 56th, and 90th days using Lysinibacillus sphaericus solution as mixing water and curing media. Commercial OPC and PPC mortar prisms cast and cured using distilled water were used as controls. Results showed that prisms treated with bacteria exhibited the highest performance on compressive strength development. Further microstructure analysis of blended cement incorporated with Lysinibacillus sphaericus bacteria showed significant amounts of reacted secondary cementitious materials compared to samples without bacteria. Bacteria presence was also found to reduce water demand during mixing and setting times and exhibited low porosity in relation to samples without bacteria. These results showed that the presence of alkaliphilic bacteria in the blended cement resulted in synergistic effect in enhancing the physicochemical and mechanical properties.

The world’s growing population and industrialization have led to increased construction activities. This has increased the amount of waste aggregates which can be recycled in construction and cut the cost of infrastructure development. This study, therefore, reports the experimental findings for the effect of immobilizing Bacillus megaterium on the compressive strength and water absorption of laboratory prepared test mortar. Bacterial solution used in this work had a concentration of 1.0 × 107 cells/mL. The impact of recycled mortar impregnated with bacteria was studied after curing the specimens in water, saturated lime water, and 1.5% sulfuric acid. Compressive strength for test specimens cured in the three media was determined at the 2nd, 7th, 28th, and 56th day of curing. SEM analysis was done for mortars cured in acidic media and saturated lime water after curing for 28 days. The test results indicated that curing in water and saturated water improved the compressive strength, while the acidic medium lowered it. Recycled mortar is, therefore, an ideal material for immobilizing Bacillus megaterium before introduction into fresh concrete/mortar. The use of recycled mortar is a good strategy to reduce wastes from construction activities, save on the cost of construction materials, and enhance environmental conservation.

We surveyed the birds of East Kwaio, Malaita, Solomon Islands from 20 October to 2 November 2018. We conducted 66 point counts and recorded or observed 58 species of resident landbirds, including 23 of the 24 passerine species known from the island of Malaita and 15 waterbird species. We collected some form of samples (e.g., whole specimens and/or blood samples) from 61 individuals of 17 species, including representatives of the four species-level endemics: Malaita Fantail Rhipidura malaitae (Mayr, 1931), Malaita Dwarf-Kingfisher Ceyx malaitae (Mayr, 1935), Malaita White-eye Zosterops stresemanni (Mayr, 1931), and Red-bellied Myzomela Myzomela malaitae (Mayr, 1931). We demonstrate the considerable potential for conservation of the Malaitan avifauna on traditional lands in the mountains of East Kwaio. The extensive knowledge of the local people was a key factor in the success of the expedition. To facilitate ongoing conservation efforts, we documented the local Kwaio names of the birds we encountered.

Summary: The fate of protective immunity following mild severe acute respiratory syndrome-coronavirus-2 (SARS-CoV-2) infection remains ill defined. Here, we characterize antibody responses in a cohort of participants recovered from mild SARS-CoV-2 infection with follow-up to 6 months. We measure immunoglobulin A (IgA), IgM, and IgG binding and avidity to viral antigens and assess neutralizing antibody responses over time. Furthermore, we correlate the effect of fever, gender, age, and time since symptom onset with antibody responses. We observe that total anti-S trimer, anti-receptor-binding domain (RBD), and anti-nucleocapsid protein (NP) IgG are relatively stable over 6 months of follow-up, that anti-S and anti-RBD avidity increases over time, and that fever is associated with higher levels of antibodies. However, neutralizing antibody responses rapidly decay and are strongly associated with declines in IgM levels. Thus, while total antibody against SARS-CoV-2 may persist, functional antibody, particularly IgM, is rapidly lost. These observations have implications for the duration of protective immunity following mild SARS-CoV-2 infection.

BackgroundCoronavirus disease 2019 (COVID-19) is associated with endothelial activation and coagulopathy, which may be related to pre-existing or infection-induced pro-thrombotic autoantibodies such as those targeting angiotensin II type I receptor (AT1R-Ab).MethodsWe compared prevalence and levels of AT1R-Ab in COVID-19 cases with mild or severe disease to age and sex matched negative controls utilizing multivariate logistic and quantile regression adjusted for comorbidities including hypertension, diabetes, and heart disease.ResultsThere were trends toward increased prevalence (50% vs. 33%, p = 0.1) and level of AT1R-Ab (median 9.8 vs. 6.1 U/mL, p = 0.06) in all cases versus controls. When considered by COVID-19 disease severity, there was a trend toward increased prevalence of AT1R-Ab (55% vs. 31%, p = 0.07), as well as significantly higher AT1R-Ab levels (median 10.7 vs. 5.9 U/mL, p = 0.03) amongst individuals with mild COVID-19 versus matched controls. In contrast, the prevalence (42% vs. 37%, p = 0.9) and level (both medians 6.7 U/mL, p = 0.9) of AT1R-Ab amongst those with severe COVID-19 did not differ from matched controls.ConclusionsThese findings support an association between COVID-19 and AT1R-Ab, emphasizing that vascular pathology may be present in individuals with mild COVID-19 as well as those with severe disease.

Efforts to reduce pressure on use of wood in particleboard formulation have included the use of non-wood materials such as crop residues. Physical and mechanical properties are determined by the number of the hydroxyl (-OH) groups. Hydroxyl (-OH) groups attracts water molecules through hydrogen bonding affecting water absorption (WA) and thickness swelling (TS). WA and TS affect curing process of adhesive. Curing process of adhesives affects the mechanical characteristics of formulated particleboards. These challenges have been acted upon continuously through research. This review paper presents crop residues used as alternative lignocellulose material source in particleboard formulation and the various advances that have been made to improve on the properties of the resultant particleboards. Improvement over time of the non-wood material in composite materials focusses on increasing water resistance and compatibility between lignocellulose and binder. Crop residues-based are used in making medium and low density particleboards. These boards have shown good mechanical characteristics which include modulus of rupture (MOR), modulus of elasticity (MOE) and internal bonding (IB). MOR, MOE and IB have over time been improved by enhancing chemical compatibility of lignocellulose material and the binders. Water absorption and thickness swelling remain challenge. This review paper further explored various methods of improving water absorption and thickness swelling of crop-residue based particleboards.

Conventional binders in the particleboards formulation involve use of formaldehyde resins. Epidemiologic studies show that formaldehyde is carcinogenic. Efforts to reduce formaldehyde emissions by use of scavengers has not been proven to reduce the emission. Molecular bonding of biobased adhesive molecules with lignocellulose materials provides an alternative way of producing composite material. In this study, maize stalk (MS), rice husks (RH) and sugarcane bagasse (SB) were used as sources of lignocellulose materials for particleboard formulation. SB, MS and RH were collected from their respective sites, sorted and dried. MS and RH were ground. Lignin content determination was done by drying lignocellulose material at 105 °C. Lignocellulose materials were prepared by hydrolysis of dried lignocellulose material with sodium hydroxide. Oxidized starch was prepared by oxidation of cassava peel starch using alkaline hydrogen peroxide. Particleboards were formulated through starch-lignocellulose polymerization at 60 °C compressed with 6.5 Nmm−2 pressure. Characterization of raw materials and formulated particleboards was done using XRD for mineralogical analysis, FTIR and NMR for elucidation of functional groups transformation. The results showed that esterification is the main process of chemical bonding in the particleboard formulation due to reaction between –COOH from starch and and OH- from lignocellulose. Etherification between hydroxyl groups from starch with hydroxyl groups from lignocellulose material. RH combined more through silication process with cassava peels starch than RH and SB showing materials containing high cellulose and hemicellulose content are more compatible. Composite materials formulated were used to produce medium density particleboards that can be used for making furniture and room partitioning.

Coevolution frequently plays an important role in diversification, but the role of obligate pollination mutualisms in the maintenance of hybrid zones has rarely been investigated. Like most members of the genus Yucca, the two species of Joshua tree (Yucca brevifolia and Yucca jaegeriana) are involved in a tightly coevolved mutualism with yucca moths. There is strong evidence of a history of coevolution between Joshua trees and their moth pollinators. We use a geographic clines approach in the Joshua tree hybrid zone to ask if selection by the moths may currently contribute to maintaining separation between these species. We compare genomic, phenotypic, and pollinator frequency clines to test whether pollinators maintain the hybrid zone or follow it as passive participants. The results reveal dramatic overlapping genomic and pollinator clines, consistent with a narrow hybrid zone maintained by strong selection. Wider phenotypic clines and a chloroplast genomic cline displaced opposite the expected direction suggest that pollinators are not the main source of selection maintaining the hybrid zone. Rather, it seems that high levels of reproductive isolation, likely acting through multiple barriers and involving many parts of the genome, keep the hybrid zone narrow.

In many countries large deposits of copper with no locally established copper based industries occur because known methods for extraction are prohibitively expensive and unaffordable. This study reports on an affordable and sustainable method for the extraction of copper. This was achieved through the use of a wet chemical method which makes use of hydrazones prepared in situ from chicken dung leached solution. The method involves the reduction of copper (II) ions leached from copper ore to zero valence using chlorine treated solution prepared from chicken droppings at a temperature range of 60–70 °C. The ore samples were pulverized to 250 micro millimetres and leached with hydrochloric acid to obtain leachate containing copper ions. The dissolved copper was reduced to copper metal and obtained by filtration. It was confirmed by XRFS analysis that, the metal purity was found to range between 60 and 80% depending on the ore used. In another experiment, chicken waste solution was used to extract copper from the ore. To the mixture, chlorine gas was then bubbledthrough a glass delivery tube to prepare the hydrazone in situ at a temperature range of 60–70 °C and a pure copper metal was obtained. The findings from this study have shown that there is great potential for the production of copper at low cost and this could be applied in both small-scale cottage industries and large industries using readily available resources such as chicken dung. Keywords: Hydrazones, In situ, Reduction, Zero valence, Chicken dung

Most of concrete structural failures are attributed to poor workmanship and poor engineering designs. Some microorganisms present in sewer systems can degrade the concrete and/or mortar. Concrete failures due to microbial attack has not attracted much attention especially in developing countries such as Kenya. This study investigated the effect of Thiobacillus intermedius bacteria on the performance of Ordinary Portland Cement (OPC). Preparation of test mortar prisms was done using the bacterial solution as either mix water, curing water or both. The control mortar prisms were prepared and cured in distilled water. Compressive strength test was done after 7th, 28th, 56th and 90th days of curing respectively. Results showed significant drop in compressive strength for the mortar prisms prepared and cured in bacterial solution as compared to the control mortar samples. Soundness and normal consistency increased significantly for the bacterial treated cement paste as compared to the control sample. Scanning Electron Microscopy (SEM) analysis showed severe damage on the bacterial treated cement mortar. This was characterized by formation of deleterious expansive products like ettringite and gypsum. Control mortar sample exhibited even formation of hydration products within the pore system.

Copper is found in several minerals in the earth's crust with varying the elemental and mineralogical composition. Several techniques of extraction have been investigated all in the effort of obtaining a cheaper and viable method. This paper reports on further works done on copper extraction using a wet chemical method. According to the method, reduction of copper (II) ions using hydrazones from chlorinated chicken waste leachate was stoichiometrically driven. The chicken dung leachate used was an impure bio-material in which the concentration could not be determined. It was, therefore, difficult to quantify the stoichiometric ratios of species in that reaction. This paper reports on a method of monitoring the extent of copper reduction by chlorinated chicken dung leachate using an aluminum electrode as an indicator. Mineral rocks were obtained from Maragwa Location in Tharaka Nithi County in Kenya. The samples were ground into a fine powder of 250 micro millimeters. The samples were then subjected to mineralogical analysis using X-ray diffraction (XRD). Chemical analysis was done using atomic absorption spectroscopy (AAS) and X-ray fluorescence spectroscopy (XRFS). Ground samples were leached using 1.0 M hydrochloric acid. The resulting leachate was treated with chicken dung leachate prepared from chicken dung in which chlorine gas was bubbled at a constant temperature of 28 °C. The pH of the resultant chicken dung leachate was adjusted from 4 to 12 using 1.0 M sodium hydroxide and then used as an electrolyte. An electrochemical cell was set up consisting of aluminum and graphite rods. The aluminum electrode was found not to corrode at pH above 11 while it was able to displace available copper ions. This property of the aluminum electrode was used to monitor when all copper ions were displaced. The recovered copper was analyzed using XRFS. The copper recovery rate from the samples ranged from 7.0 to 20.0 at level A and 7.4–26.8% at level B with a purity range of 84.9 level A to 88.6% level B. An overall positive potential in the reduction process confirmed the greater the tendency of copper reduction without an external source of electricity. The corrosion of the aluminium electrode in the process was not observed and therefore does not require frequent replacement. Therefore, a large scale extraction process needs to be investigated.

Recovery efficiency is a key factor in decision-making in oil and gas projects. Although structural setup and well type considerably influence waterflood recovery, few studies have explored the performance of highly deviated wells during the waterflooding of complex shallow reservoirs. Here, we applied numerical simulations to investigate the performance of vertical, horizontal, multilateral, and highly deviated wells during waterflooding of complex shallow reservoirs using the J1 Oilfield as a case study. Recovery efficiencies of 31%, 33%, 31%, and 26% could be achieved for vertical, horizontal, multilateral, and highly deviated wells, respectively. The gas production rate was 39% higher in the vertical wells than in the other types. Highly deviated wells yielded the highest water-cut (80%) over a short period. Highly deviated wells delivered the least production, and, despite branching laterals, multilateral wells were also not the most productive. Our results provide insights into the performance of different well types during the waterflooding of green heterogeneous non-communicating reservoirs and present an example of the successful practical application of waterflooding as an initial recovery mechanism when oil is near the bubble point. This study indicated that multilateral wells are not a panacea in reservoir development. Highly deviated wells are the ideal choice for the shallow, heterogeneous non-communicating reservoirs when economic and environmental impact are considered in decision-making. Well design should be a case-by-case study considering reservoir characteristics, economics, and environment impact.

Formaldehyde-based resins are conventionally used as a binder in formulation of particleboard. Epidemiologic studies have shown that formaldehyde is carcinogenic. Efforts to reduce the health hazard effects of the fomaldehyde-based resin in the particleboard formulation have included use of scavengers for formaldehydes and use of an alternative binder. Use of scavengers for the formaldehyde increases the cost and maintenance of particleboard formulation. There is no proof that scavengers eliminate the emission of formaldehyde from particleboard. Use of biobased binders in particleboard formulation provides an alternative for eliminating use of the formaldehyde-based resin. However, the alternative is hindered by challenges, which include limitations of physical and mechanical properties. The challenge has continuously been acted upon through research. The paper presents an overview of the use of starch as an alternative binder. Improvement over time of the starch and limitations thereof requires to be addressed. Use of the modified starch has shown increased particleboard performance. Mechanical strength, such as modulus of rupture, modulus of elasticity, and internal bonding in particleboards, however, remains to be a challenge.

Conventional methods of making particleboards utilize wood chips. This has resulted in a decrease in the tree cover due to the increase in wood demand. The effect has been climatic change. Wood is bound using phenol formaldehyde resin. Because of the decrease in the forest cover, alternative lignocellulose materials are required. In this study, lignocellulose materials used include sugarcane bagasse, maize stock, and rice husks. The cassava-starch mix with borax was used as a binder in particleboard formulation. The lignin content was determined, and its effect on properties of boards was investigated. The resultant composite material was molded at a pressure of 6.5 N/mm2 and at 30°C. The resultant particleboards had mean densities ranging from 0.604 to 0.611 g/cm3. The modulus of elasticity ranged from 2364.2 N/mm2 to 3329.93 N/mm2, modulus of rupture ranged from 13.55 N/mm2 to 14.83 N/mm2, and internal bonding ranged from 1.613 N/mm2 to 2.370 N/mm2. The performance of the board was dependent on the lignocellulose material used. Fourier transform infrared spectroscopy analysis showed that main chemical bonding in the particleboard resulted from esterification of –COOH from lignocellulose and OH- from starch. The particleboards formulated were found to be of low-density-fibre standard used in a similar manner to the conventional low-density particleboards.

When a university-mandated ‘Better Teaching Better Learning’ agenda targeted at unit enhancement coincided with a whole of curriculum review, law lecturers teaching first year law units at Monash University piloted a ‘semi-flipped’ series of short videos, supported by online and in-class activities, in order to incorporate blended learning design in key foundation units. This paper examines the key issues in the design, and implementation and evaluation of the ‘semi-flipped’ experience, highlighting lessons learnt, in terms of technical support, pedagogical issues and assessment considerations. In particular, the utility in seeking to evaluate students’ learning outcomes, engagement with reading materials and in-class activities is critically considered.

Australian legal educators have been singing the praises of clinical legal education loud and clear in recent years. Moreover, a significant percentage of Australian law schools have introduced diverse clinical education programs. While it is widely accepted that clinical subjects are a welcome addition to the modern law student experience, it is contended that there are varied perspectives on the appropriate function and design of clinical subjects and programs. The purpose of this paper is to conceptualise these diverse perspectives by examining clinical legal education through the lens of legal education discourse. Legal education is characterised by distinct and competing discourses with respect to the nature of law teaching, including doctrinalism, vocationalism, corporatism, liberalism, radicalism and educationalism. The first part of the paper provides an overview of Foucauldian discourse theory and a description of each legal education discourse. The second part of the paper provides an analysis of clinical legal education in the context of each discourse, illustrating the distinctive features of CLE that are aligned and misaligned with the fundamental tenets of each discourse. An introduction to legal education discourse serves to provide law teachers with a sense of objective clarity regarding the competing perspectives that characterise typical law school debates on matters of pedagogy, such as clinical legal education.

Numerous US drinking water aquifers have been contaminated with per- and polyfluoroalkyl substances (PFAS) from fire-fighting and fire-training activities using aqueous film-forming foam (AFFF). These sites often contain other organic compounds, such as fuel hydrocarbons and methane, which may serve as primary substrates for cometabolic (i.e., nongrowth-linked) biotransformation reactions. This work investigates the abilities of AFFF site relevant bacteria (methanotrophs, propanotrophs, octane, pentane, isobutane, toluene, and ammonia oxidizers), known to express oxygenase enzymes when degrading their primary substrates, to biotransform perfluoroalkyl acid (PFAA) precursors to terminal PFAAs. Microcosms containing AFFF-impacted groundwater, 6:2 fluorotelomer sulfonate (6:2 FTS), or N -ethylperfluorooctane sulfonamidoethanol (EtFOSE) were inoculated with the aerobic cultures above and incubated for 4 and 8 weeks at 22 °C. Bottles were sacrificed, extracted, and subjected to target, nontarget, and suspect screening for PFAS. The PFAA precursors 6:2 FTS, N-sulfopropyldimethyl ammoniopropyl perfluorohexane sulfonamide (SPrAmPr-FHxSA), and EtFOSE transformed up to 99, 71, and 93%, respectively, and relevant daughter products, such as the 6:1 fluorotelomer ketone sulfonate (6:1 FTKS), were identified in quantities previously not observed, implicating oxygenase enzymes. This is the first report of a suite of site relevant PFAA precursors being transformed in AFFF-impacted groundwater by bacteria grown on substrates known to induce specific oxygenase enzymes. The data provide crucial insights into the microbial transformation of these compounds in the subsurface.

To date, life support systems on the International Space Center (ISS) or those planned for upcoming moon/Mars missions have not included biological reactors for wastewater treatment, despite their ubiquitous use for the treatment of terrestrial wastewaters. However, the new focus on partial gravity habitats reduces the required complexity of treatment systems compared with those operating in micro-gravity, and the likely addition of large-volume wastewaters with surfactant loads (e.g., laundry and shower) makes the current ISS wastewater treatment system inappropriate due to the foaming potential from surfactants, increased consumable requirements due to the use of non-regenerative systems (e.g., mixed adsorbent beds), the complexity of the system, and sensitivity to failures from precipitation and/or biological fouling. Hybrid systems that combine simple biological reactors with desalination (e.g., Reverse Osmosis (RO)) could reduce system and consumable mass and complexity. Our objective was to evaluate a system composed of a membrane-aerated bioreactor (MABR) coupled to a low-pressure commercial RO system to process partial gravity habitat wastewater. The MABR was able to serve as the only wastewater collection tank (variable volume), receiving all wastewaters as they were produced. The MABR treated more than 20,750 L of graywater and was able to remove more than 90% of dissolved organic carbon (DOC), producing an effluent with DOC < 14 mg/L and BOD < 12 mg/L and oxidizing >90% of the ammoniacal nitrogen into NOx - . A single RO membrane (260 g) was able to process >3000 L of MABR effluent and produced a RO permeate with DOC < 5 mg/L, TN < 2 mg/L, and TDS < 10 mg/L, which would essentially meet ISS potable water standards after disinfection. The system has an un-optimized mass and volume of 128.5 kg. Consumables include oxygen (~4 g/crew-day), RO membranes, and a prefilter (1.7 g/crew-day). For a one-year mission with four crew, the total system + consumable mass are ~141 kg, which would produce ~15,150 kg of treated water, resulting in a pay-back period of 13.4 days (3.35 days for a crew of four). Given that the MABR in this study operated for 500 days, while in previous studies, similar systems operated for more than 3 years, the total system costs would be exceedingly low. These results highlight the potential application of hybrid treatment systems for space habitats, which may also have a direct application to terrestrial applications where source-separated systems are employed.

The assessment of a cap for remediation of sediments requires long-term monitoring because of the slow migration of contaminants in porous media. In this study, coring and passive sampling tools were used to assess the transport and degradation of polycyclic aromatic hydrocarbons (PAHs) in an amended cap (sand + Organoclay® PM-199) in the Grand Calumet River (Indiana, USA) during four sampling events from 2012 to 2019. Measurements of three PAHs (phenanthrene (Phe), pyrene (Pyr) and benzo[a]pyrene (BaP), representing low, medium, and high molecular weight compounds, respectively) showed a difference of at least two orders of magnitude between bulk concentrations in the native sediments and the remediation cap. Averages of pore water measurements also showed lower levels in the cap respective to the native sediments by a factor of at least 7 for Phe and 3 for Pyr. In addition, between the baseline (BL), which corresponds to observations from 2012 to 2014, and the measurements in 2019, there was a decrease in depth-averaged pore water concentrations of Phe (C 2019 /C BL =0.20 -0.07 +0.12 in sediments and 0.27 -0.10 +0.15 in cap) and Pyr (C 2019 /C BL =0.47 -0.12 +0.16 in sediments and 0.71 -0.20 +0.28 in the cap). In the case of BaP in pore water, no change was observed in native sediments (C 2019 /C BL =1.0 -0.24 +0.32 ) and there was an increase in the cap (C 2019 /C BL =2.0 -0.54 +0.72 ). Inorganic anions and estimates of pore water velocity along with measurements of PAHs were used to model the fate and transport of contaminants. The modeling suggested that degradation of Phe (t 1/2 =1.12 -0.11 +0.16 years) and Pyr (t 1/2 =5.34 -1.8 +5.3 years) in the cap is faster than migration, thus the cap is expected to be protective of the sediment-water interface indefinitely for these constituents. No degradation was noted in BaP and the contaminant is expected to reach equilibrium in the capping layer over approximately 100 years if there exists sufficient mass of BaP in the sediments and there is no deposition of clean sediment at the surface., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: W. Andrew Jackson reports financial support was provided by the Environmental Security Technology Certification Program (ESTCP, US). Danny Reible reports financial support was provided by the USEPA., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Although many studies have assessed the bioaccumulation of perfluoroalkyl substances (PFAS) in plant tissues, to date there has been minimal research on the bioaccumulation of PFAS in soil invertebrates that results from consuming PFAS-contaminated media. The present study focused on two different consumption pathways in a population of crickets: individuals consuming PFAS-contaminated alfalfa and individuals consuming PFAS-spiked drinking water. Alfalfa was grown in a greenhouse and irrigated with PFAS-spiked water (∼1 ppm) containing seven unique PFAS. The alfalfa was then harvested and fed to crickets. Another population of crickets was supplied with PFAS-spiked drinking water at similar concentrations to irrigation water for direct consumption. Alfalfa accumulation of PFAS and subsequent consumption by the crickets resulted in overall similar tissue concentrations in the crickets who consumed PFAS-spiked water directly. This indicates that source concentration (water) may be an important factor in assessing the bioaccumulation of PFAS in organisms. To our knowledge, ours is the first study not only to assess the direct trophic transfer of PFAS from contaminated vegetation to invertebrates, but also to highlight the similarities in bioaccumulation regardless of ingestion pathway. Environ Toxicol Chem 2022;41:2981-2992. © 2022 SETAC., (© 2022 SETAC.)

This study contrasts the use of high-resolution passive sampling and traditional groundwater monitoring wells (GWMW) to characterize a chlorinated solvent site and assess the effectiveness of a biowall (mulch, compost and sand) that was installed to remediate trichloroethene (TCE), the primary contaminant of concern. High-resolution passive profilers (HRPPs) were direct driven hydraulically upgradient, within, and hydraulically downgradient of the biowall and in close proximity to existing GWMWs. Compared with hydraulically upgradient locations, the biowall was highly reducing, there were higher densities of bacteria/genes capable of reductive dechlorination, and TCE was being reductively transformed, but not completely, as cis-1,2-dichloroethene (cis-DCE) was detected within and hydraulically downgradient of the biowall. However, based on the high-resolution data, there were a number of important findings which were not discoverable using data from GWMWs alone. Data from the HRPPs indicate that the biowall was completely transforming TCE to ethene (C 2 H 4 ) except within a high velocity interval, where the concentrations were reduced, but breakthrough of cis-DCE was apparent. Hydraulically upgradient of the biowall, concentrations of TCE increased with depth where a very low permeability zone exists that will likely remain as a long-term source. In addition, although low concentrations of cis-DCE were present downgradient of the biowall, surfacing into a downgradient stream was not detected. This study demonstrates the advantages of high-resolution passive sampling of aquifers to assess the performance of remediation techniques compared to traditional methods such as GWMWs., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) are globally distributed and present in nearly every environmental compartment. Characterizing the chronic toxicity of individual PFAS compounds and mixtures is necessary because many have been reported to cause adverse health effects. To derive toxicity reference values (TRVs) and conduct ecotoxicological risk assessments (ERAs) of PFAS-contaminated ecosystems for wildlife, species-specific PFAS chronic toxicity values (CTVs) are needed. The present study quantified PFAS residues from liver and eggs of birds chronically exposed to perfluorohexanoic acid (PFHxA) or a mixture of perfluorooctane sulfonate (PFOS) and PFHxA that produced a no-observable-adverse-effect level (NOAEL) and/or a lowest-observable-adverse-effectlevel (LOAEL). The CTVs we present are lower than those previously reported for birds and should be considered in future regulatory evaluations. From the estimated species- and tissue-specific PFAS CTVs, we found that PFOS and perfluorohexane sulfonate (PFHxS) were more bioaccumulative than PFHxA in avian tissues, but PFHxA was more toxic to reproducing birds than either PFOS or a PFOS:PFHxS mixture. We further determined that avian toxicity was not necessarily additive with respect to PFAS mixtures, which could have implications for PFAS ERAs. The PFAS LOAEL CTVs can be used to predict reproductive and possible population-level adverse health effects in wild avian receptors. Environ Toxicol Chem 2022;41:219-229. © 2021 SETAC., (© 2021 SETAC.)

Terrestrial toxicology data are limited for comprehensive ecotoxicological risk assessment of ecosystems contaminated by per- and polyfluoroalkyl substances (PFAS) partly because of their existence as mixtures in the environment. This complicates logistical dose-response modeling and establishment of a threshold value characterizing the chronic toxicity of PFAS to ecological receptors. We examined reproduction, growth, and survival endpoints using a combination of hypothesis testing and logistical dose-response modeling of northern bobwhite quail (Colinus virginianus) exposed to perfluorohexanoic acid (PFHxA) alone and to PFHxA in a binary mixture with perfluorooctane sulfonic acid (PFOS) via the drinking water. The exposure concentration chronic toxicity value (CTV) representative of the lowest-observable-adverse effect level (LOAEL) threshold for chronic oral PFAS toxicity (based on reduced offspring weight and growth rate) was 0.10 ng/mL for PFHxA and 0.06 ng/mL for a PFOS:PFHxA (2.7:1) mixture. These estimates corresponded to an adult LOAEL average daily intake CTV of 0.0149 and 0.0082 µg × kg body weight -1  × d -1 , respectively. Neither no-observable-adverse effect level threshold and representative CTVs nor dose-response and predicted effective concentration values could be established for these 2 response variables. The findings indicate that a reaction(s) occurs among the individual PFAS components present in the mixture to alter the potential toxicity, demonstrating that mixture affects avian PFAS toxicity. Thus, chronic oral PFAS toxicity to avian receptors represented as the sum of the individual compound toxicities may not necessarily be the best method for assessing chronic mixture exposure risk at PFAS-contaminated sites. Environ Toxicol Chem 2021;40:2601-2614. © 2021 SETAC., (© 2021 SETAC.)

A new method has been developed to determine trace amounts of phosphite (HPO 3 -2 ) in environmental samples using ion chromatography with electrospray tandem mass spectrometry (IC-ESI/MS/MS). The method includes the production and use of an 18 O-labeled HPO 3 -2 internal standard (IS). This isotopically labeled IS significantly improved sensitivity and could account for matrix suppression. The method detection limit (MDL) was determined as 0.017 and 0.034 μg L -1 of HPO 3 -2 (6.5 and 13 ng P L -1 ) using a 500 and 25 μL injection loop, respectively. Precision (1-10%) and accuracy (recoveries = 96-106%) were established for a range of environmental samples using known (spiked) addition. The impact of ionic interferences was investigated by evaluating the response of the internal standard in the presence of common anions with respect to distilled deionized water. The most significant interference was due to nitrate (100 mg-NO 3 - L -1 ) with a 99.99% reduction in IS intensity. The method was successfully applied to wastewater effluent, surface water, tap water, and soil samples. Relatively low concentrations <0.25 μg HPO 3 -2  L -1 were measured in tap water, surface water and wastewater effluent, and ~1.6 μg kg -1 HPO 3 -2 in soil samples, using both injection loops. Limited suppression was observed for all matrices. The largest IS peak area suppression (~98%) was observed in WW effluent with 500 μL injection loop; however, this method was able to quantify HPO 3 -2 with good recoveries and precision despite the mentioned suppression, supporting the ability of the proposed method to quantify HPO 3 -2 in different environmental matrices., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

Natural chlorate (ClO 3 - ) is widely distributed in terrestrial and extraterrestrial environments. To improve understanding of the origins and distribution of ClO 3 - , we developed and tested methods to determine the multi-dimensional isotopic compositions (δ 18 O, Δ 17 O, δ 37 Cl, 36 Cl/Cl) of ClO 3 - and then applied the methods to samples of natural nitrate-rich caliche-type salt deposits in the Atacama Desert, Chile, and Death Valley, USA. Tests with reagents and artificial mixed samples indicate stable-isotope ratios were minimally affected by the purification processes. Chlorate extracted from Atacama samples had δ 18 O = +7.0 to +11.1‰, Δ 17 O = +5.7 to +6.4‰, δ 37 Cl = -1.4 to +1.3‰, and 36 Cl/Cl = 48 × 10 -15 to 104 × 10 -15 . Chlorate from Death Valley samples had δ 18 O = -6.9 to +1.6‰, Δ 17 O = +0.4 to +2.6‰, δ 37 Cl = +0.8 to +1.0‰, and 36 Cl/Cl = 14 × 10 -15 to 44 × 10 -15 . Positive Δ 17 O values of natural ClO 3 - indicate that its production involved reaction with O 3 , while its Cl isotopic composition is consistent with a tropospheric or near-surface source of Cl. The Δ 17 O and δ 18 O values of natural ClO 3 - are positively correlated, as are those of ClO 4 - and NO 3 - from the same localities, possibly indicating variation in the relative contributions of O 3 as a source of O in the formation of the oxyanions. Additional isotopic analyses of ClO 3 - could provide stronger constraints on its production mechanisms and/or post-formational alterations, with applications for environmental forensics, global biogeochemical cycling of Cl, and the origins of oxyanions detected on Mars., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Osteoid osteomas account for approximately 3% to 10% of primary bone tumors and are found most commonly in the cortical, diaphyseal regions of long tubular bones. These osteoblastic, benign tumors are usually seen in males, in the second to third decade, most often in the long bones of the lower extremity. The literature describes the limited encounters with osteoid osteomas of the pedal digital phalanx, especially in the pediatric population. Here, a case report details a juvenile patient with an osteoid osteoma tumor of the distal phalanx in the right second digit that was treated with complete distal phalanx excision in toto, eliminating the patient's pain and symptoms quickly after surgery. Further the literature is reviewed for other examples of this pathology in the similar clinical setting.

The fate and transport of groundwater contaminants depends partially on groundwater velocity, which can vary appreciably in highly stratified aquifers. A high-resolution passive profiler (HRPP) was developed to evaluate groundwater velocity, contaminant concentrations, and microbial community structure at ∼20 cm vertical depth resolution in shallow heterogeneous aquifers. The objective of this study was to use mass transfer of bromide (Br - ), a conservative tracer released from cells in the HRPP, to estimate interstitial velocity. Laboratory experiments were conducted to empirically relate velocity and the mass transfer coefficient of Br - based on the relative loss of Br - from HRPP cells. Laboratory-scale HRPPs were deployed in flow boxes containing saturated soils with differing porosities, and the mass transfer coefficient of Br - was measured at multiple interstitial velocities (0 to 100 cm/day). A two-dimensional (2D) quasi-steady-state model was used to relate velocity to mass transfer of Br - for a range of soil porosities (0.2-0.5). The laboratory data indicate that the mass transfer coefficient of Br - , which was directly-but non-linearly-related to velocity, can be determined with a single 3-week deployment of the HRPP. The mass transfer coefficient was relatively unaffected by sampler orientation, length of deployment time, or porosity. The model closely simulated the experimental results. The data suggest that the HRPP will be applicable for estimating groundwater velocity ranging from 1 to 100 cm/day in the field at a minimum depth resolution of 10 cm, depending on sampler design., (© 2019, National Ground Water Association.)

The presence of perchlorate on Mars suggests a possible energy source for sustaining microbial life. Perchlorate-reducing microbes have been isolated from perchlorate-contaminated soils and sediments on the Earth, but to date, never from an environment that is naturally enriched in perchlorate. The arid Pilot Valley paleolake basin in Utah is a Mars analog environment whose sediments are naturally enriched with up to ∼6.5 μg kg -1 perchlorate oxyanions. Here, we present results of field and laboratory studies indicating that perchlorate-reducing microorganisms co-occur with this potential electron acceptor. Biogeochemical data suggest ongoing perchlorate reduction; phylogenetic data indicate the presence of diverse microbial communities; and laboratory enrichments using Pilot Valley sediments show that resident microbes can reduce perchlorate. This is the first article of the co-existence of perchlorate-reducing microbes in an environment where perchlorate occurs naturally, arguing for Pilot Valley's utility as an analog for studying biogeochemical processes that may have occurred, and may yet still be occurring, in ancient martian lacustrine sediments.

Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth environments and consequently in food supplies., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Due to the high volume of crude oil released by the Deepwater Horizon oil spill, the salt marshes along the gulf coast were contaminated with crude oil. Biodegradation of crude oil in salt marshes is primarily limited by oxygen availability due to the high organic carbon content of the soil, high flux rate of S(2-), and saturated conditions. Chlorate, nitrate, and perchlorate were evaluated for use as electron acceptors in comparison to oxygen by comparing oil transformation and mineralization in mesocosms consisting of oiled salt marsh sediment from an area impacted by the BP Horizon oil spill. Mineralization rates were determined by measuring CO2 production and δ (13)C of the produced CO2 and compared to transformation evaluated by measuring the alkane/hopane ratios over a 4-month period. Total alkane/hopane ratios decreased (~55-70 %) for all treatments in the following relative order: aerated ≈ chlorate > nitrate > perchlorate. Total CO2 produced was similar between treatments ranging from 550-700 mg CO2-C. The δ (13)C-CO2 values generally ranged between the indigenous carbon and oil values (-17 and -27‰, respectively). Oil mineralization was greatest for the aerated treatments and least for the perchlorate amended. Our results indicate that chlorate has a similar potential as oxygen to support oil mineralization in contaminated salt marshes, but nitrate and perchlorate were less effective. The use of chlorate as a means to promote oil mineralization in situ may be a promising means to remediate contaminated salt marshes while preventing unwanted secondary impacts related to nutrient management as in the case of nitrate amendments.

Stream-dwelling species in the U.S. southern Appalachian Mountains region are particularly vulnerable to climate change and acidification. The objectives of this study were to quantify the spatial extent of contemporary suitable habitat for acid- and thermally sensitive aquatic species and to forecast future habitat loss resulting from expected temperature increases on national forest lands in the southern Appalachian Mountain region. The goal of this study was to help watershed managers identify and assess stream reaches that are potentially vulnerable to warming, acidification, or both. To our knowledge, these results represent the first regional assessment of aquatic habitat suitability with respect to the combined effects of stream water temperature and acid-base status in the United States. Statistical models were developed to predict July mean daily maximum water temperatures and air-water temperature relations to determine potential changes in future stream water temperatures. The length of stream considered suitable habitat for acid- and thermally sensitive species, based on temperature and acid neutralizing capacity thresholds of 20°C and 50 μeq/L, was variable throughout the national forests considered. Stream length displaying temperature above 20°C was generally more than five times greater than the length predicted to have acid neutralizing capacity below 50 μeq/L. It was uncommon for these two stressors to occur within the same stream segment. Results suggested that species' distributional shifts to colder, higher elevation habitats under a warming climate can be constrained by acidification of headwater streams. The approach used in this study can be applied to evaluate climate change impacts to stream water resources in other regions.

Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean.

Perchlorate (ClO) is a contaminant that occurs naturally throughout the world, but little is known about its distribution and interactions in terrestrial ecosystems. The objectives of this Amargosa Desert, Nevada study were to determine (i) the local-scale distribution of shallow-soil (0-30 cm) ClO with respect to shrub proximity (far and near) in three geomorphic settings (shoulder slope, footslope, and valley floor); (ii) the importance of soil, plant, and terrain variables on the hillslope-distribution of shallow-soil and creosote bush [ (Sessé & Moc. ex DC.) Coville] ClO; and (iii) atmospheric (wet plus dry, including dust) deposition of ClO in relation to soil and plant reservoirs and cycling. Soil ClO ranged from 0.3 to 5.0 μg kg. Within settings, valley floor ClO was 17× less near shrubs due in part to enhanced leaching, whereas shoulder and footslope values were ∼2× greater near shrubs. Hillslope regression models (soil, = 0.42; leaf, = 0.74) identified topographic and soil effects on ClO deposition, transport, and cycling. Selective plant uptake, bioaccumulation, and soil enrichment were evidenced by leaf ClO concentrations and Cl/ClO molar ratios that were ∼8000× greater and 40× less, respectively, than soil values. Atmospheric deposition ClO flux was 343 mg ha yr, ∼10× that for published southwestern wet-deposition fluxes. Creosote bush canopy ClO (1310 mg ha) was identified as a previously unrecognized but important and active reservoir. Nitrate δO analyses of atmospheric deposition and soil supported the leaf-cycled-ClO input hypothesis. This study provides basic data on ClO distribution and cycling that are pertinent to the assessment of environmental impacts in desert ecosystems and broadly transferable to anthropogenically contaminated systems., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Assessments of potential exposure to fullerenes and their derivatives in the environment are important, given their increasing production and use. Our study focused on fate processes that determine the movement and bioavailability of fullerenes in soil. We evaluated the sorption, biodegradation, and plant uptake of C60 fullerene using (14)C-labeled C60 solutions in water produced by either solvent exchange with tetrahydrofuran or sonication/extended mixing in water. Organic carbon appeared to have an important influence on C60 soil sorption. The log Koc values for (14)C60 were equivalent for sandy loam and silt loam (3.55 log[mL/g]) but higher for loam (4.00 log[mL/g]), suggesting that other factors, such as pH, clay content and mineralogy, and cation exchange capacity, also influence C60 soil sorption. There was little (14)CO2 production in the silt loam or the sandy loam soil after 754 and 328 days, respectively, suggesting high resistance of C60 to mineralization in soil. Plant uptake was generally low (∼7%), with most of the uptaken (14)C accumulating in the roots (40-47%) and smaller amounts of accumulation in the tuber (22-23%), stem (12-16%), and leaves (18-22%). Our results indicate that C60 released to the environment will not be highly bioavailable but will likely persist in soil for extended periods.

Perchlorate (ClO4(-)) interferes with uptake of iodide in humans. Emission inventories do not explain observed distributions. Ozone (O3) is implicated in the natural origin of ClO4(-), and has increased since pre-industrial times. O3 produces ClO4(-)in vitro from Cl(-), and plant tissues contain Cl(-) and redox reactions. We hypothesize that O3 exposure may induce plant synthesis of ClO4(-). We exposed contrasting crop species to environmentally relevant O3 concentrations. In the absence of O3 exposure, species exhibited a large range of ClO4(-) accumulation but there was no relationship between leaf ClO4(-) and O3, whether expressed as exposure or cumulative flux (dose). Older, senescing leaves accumulated more ClO4(-) than younger leaves. O3 exposed vegetation is not a source of environmental ClO4(-). There was evidence of enhanced ClO4(-) content in the soil surface at the highest O3 exposure, which could be a significant contributor to environmental ClO4(-)., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Aqueous chlorine solutions (defined as chlorine solutions (Cl(2,T)) containing solely or a combination of molecular chlorine (Cl(2)), hypochlorous acid (HOCl), and hypochlorite (OCl(-))) are known to produce toxic inorganic disinfection byproduct (e.g., chlorate and chlorite) through photoactivated transformations. Recent reports of perchlorate (ClO(4)(-)) production-a well-known thyroid hormone disruptor- from stored bleach solutions indicates the presence of unexplored transformation pathway(s). The evaluation of this potential ClO(4)(-) source is important given the widespread use of aqueous chlorine as a disinfectant. In this study, we perform detailed rate analysis of ClO(4)(-) generation from aqueous chlorine under varying environmental conditions including ultraviolet (UV) light sources, intensity, solution pH, and Cl(2,T) concentrations. Our results show that ClO(4)(-) is produced upon UV exposure of aqueous chlorine solutions with yields ranging from 0.09 × 10(-3) to 9.2 × 10(-3)% for all experimental conditions. The amount of ClO(4)(-) produced depends on the starting concentrations of Cl(2,T) and ClO(3)(-), UV source wavelength, and solution pH, but it is independent of light intensity. We hypothesize a mechanistic pathway derived from known reactions of Cl(2,T) photodecomposition that involves the reaction of Cl radicals with ClO(3)(-) to produce ClO(4)(-) with calculated rate coefficient (k(ClO4-)) of (4-40) × 10(5) M(-1) s(-1) and (3-250) × 10(5) M(-1) s(-1) for UV-B/C and UV-A, respectively. The measured ClO(4)(-) concentrations for both UV-B and UV-C experiments agreed well with our model (R(2) = 0.88-0.99), except under UV-A light exposure (R(2) = 0.52-0.93), suggesting the possible involvement of additional pathways at higher wavelengths. Based on our results, phototransformation of aqueous chlorine solutions at concentrations relevant to drinking water treatment would result in ClO(4)(-) concentrations (~0.1 μg L(-1)) much below the proposed drinking water limits. The importance of the hypothesized mechanism is discussed in relation to natural ClO(4)(-) formation by atmospheric transformations.

An important tool in the evaluation of acidification damage to aquatic and terrestrial ecosystems is the critical load (CL), which represents the steady-state level of acidic deposition below which ecological damage would not be expected to occur, according to current scientific understanding. A deposition load intended to be protective of a specified resource condition at a particular point in time is generally called a target load (TL). The CL or TL for protection of aquatic biota is generally based on maintaining surface water acid neutralizing capacity (ANC) at an acceptable level. This study included calibration and application of the watershed model MAGIC (Model of Acidification of Groundwater in Catchments) to estimate the target sulfur (S) deposition load for the protection of aquatic resources at several future points in time in 66 generally acid-sensitive watersheds in the southern Blue Ridge province of North Carolina and two adjoining states. Potential future change in nitrogen leaching is not considered. Estimated TLs for S deposition ranged from zero (ecological objective not attainable by the specified point in time) to values many times greater than current S deposition depending on the selected site, ANC endpoint, and evaluation year. For some sites, one or more of the selected target ANC critical levels (0, 20, 50, 100μeq/L) could not be achieved by the year 2100 even if S deposition was reduced to zero and maintained at that level throughout the simulation. Many of these highly sensitive streams were simulated by the model to have had preindustrial ANC below some of these target values. For other sites, the watershed soils contained sufficiently large buffering capacity that even very high sustained levels of atmospheric S deposition would not reduce stream ANC below common damage thresholds., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Pharmaceuticals and personal care products (PPCPs) have emerged as a group of potential environmental contaminants of concern. PPCPs in soil may enter terrestrial food webs via plant uptake. We evaluated uptake of 17α-ethynylestradiol (EE2) and triclosan in bean plants (Phaseolus vulgaris) grown in sand and soil. The extent of uptake and accumulation of EE2 and triclosan in plants grown in sand was higher than in plants grown in soil. In sand (conditions of maximum contaminant bioavailability), bioconcentration factors (BCFs) of EE2 and triclosan in roots (based on dry weights) were 1424 and 16,364, respectively, whereas BCFs in leaves were 55 for EE2 and 85 for triclosan. In soil, the BCF of EE2 decreased from 154 in the first week to 32 in the fourth week while it fluctuated in leaves from 18 to 20. The BCF for triclosan in plants grown in soil increased over time to 12 in roots and 8 in leaves. These results indicate that the potential for uptake and accumulation of PPCPs in plants exists. This trophic transfer pathway should be considered when assessing exposure to certain PPCPs, particularly with the use of recycled wastewater for irrigation., (Copyright © 2011 Elsevier Inc. All rights reserved.)

A modified membrane-aerated biofilm reactor (mMABR) that combined oxygen permeable membranes and inert attachment media to support both nitrification and denitrification was used to treat a carbon-limited (COD:N = 1.8) and ammonium-rich (NH4+ = 650 g-N/m3) space habitation waste stream. An eight-fold increase in intramembrane air pressure did not affect process performance; however, for an air pressure of 11 kPa (gauge), lower and upper hydraulic loading limits for the mMABR were identified at 30 g-N/m3 x d and 123 g-N/m3 x d, respectively. Oxygen limitation occurred at the highest loading rate and alkalinity limitation occurred at the lowest loading rate. Partial nitrification was noted at both limitations. Additionally, increased recirculation ratios were shown to decrease denitrification efficiency. Mean carbon and nitrogen removal rates were as high as 75.3 g-C/m3 x d (0.26 g-C/m2d) and 63.8 g-N/m3 x d (0.22 g-N/m2 x d), respectively. The mMABR achieved maximal nitrification and denitrification performance given the stoichiometric nature of the waste.

Perchlorate is ubiquitous in the environment, leading to human exposure and potential impact on thyroid function. Nitrate can also competitively inhibit iodide uptake at the sodium-iodide symporter and thus reduce thyroid hormone production. This study investigates the intake of perchlorate, nitrate, and iodide attributable to direct and indirect tap water consumption. The National Health and Nutrition Examination Survey collected tap water samples and consumption data from 3262 U.S. residents during the years 2005-2006. The median perchlorate, nitrate, and iodide levels measured in tap water were 1.16, 758, and 4.55 μg/L, respectively. Measured perchlorate levels were below the United States Environmental Protection Agency (U.S. EPA) drinking water equivalent level for perchlorate (24.5 μg/L). Significant correlations were found between iodide and nitrate levels (r = 0.17, p < 0.0001) and perchlorate and nitrate levels (r = 0.25, p < 0.0001). On the basis of 24 h recall, 47% of the study participants reported drinking tap water; 89% reported either direct or indirect consumption of tap water. For the adult population (age ≥ 20 yrs) the median tap water consumption rate was 11.6 mL/kg-day. Using individual tap water consumption data and body weight, we estimated the median perchlorate, nitrate, and iodide dose attributable to tap water as 9.11, 11300, and 43.3 ng/kg-day, respectively, for U.S. adults. This perchlorate exposure dose from tap water is relatively small compared to the total perchlorate exposure dose previously characterized for the U.S. adults (median 64 ng/kg-day) and the U.S. EPA reference dose (700 ng/kg-day).