Integrating portable X-ray fluorescence site survey and ArcGIS models for rapid risk assessment and mitigation strategies at an abandoned arsenic mine site: a case study.

Australia's metalliferous abandoned mine sites (MAMSs), pose tangible threats to the environment and human health. To address these concerns, our study utilised state-of-the-art handheld XRF technology to conduct a real-time assessment of the Mole River arsenic mine site. The data revealed notably elevated levels of arsenic and manganese, with the southeast corner of the site identified as a contaminant hotspot. We used a tiered risk assessment approach to compare the detected contaminant concentrations to the Australian health investigation levels (tier 1). This led us to a broader examination of erosion vulnerabilities and the potential migration of contaminants (tier 2). Further, a hydrological assessment (tier 3) identified significant erosion in southern regions, indicating the potential for contaminants to be transported off-site through surface water runoff to Sam's Creek and Mole River. The proximity of a reservoir to these runoff pathways brought forth additional challenges, especially during heavy rainfall events. Subsequent laboratory analysis of water samples reinforced our findings, as they confirmed heightened arsenic concentrations in Mole River downstream, accentuating the potential risks to ecosystems and human health. By integrating the XRF contour map and erosion assessment with the RUSLE model, valuable insights are gained into critical hotspots with high contamination and erosion potential. By directing rehabilitation efforts towards critical hotspots, resources can be allocated more efficiently and cost-effectively.

Controlled release herbicide formulation for effective weed control efficacy.

Controlled release formulation (CRF) of herbicide is an effective weed management technique with less eco-toxicity than other available commercial formulations. To maximise the effectiveness of CRFs however, it is crucial to understand the herbicide-releasing behaviour at play, which predominately depends on the interaction mechanisms between active ingredients and carrier materials during adsorption. In this study, we investigated and modelled the adsorption characteristics of model herbicide 2,4-D onto two organo-montmorillonites (octadecylamine- and aminopropyltriethoxysilane-modified) to synthesise polymer-based CRFs. Herbicide-releasing behaviour of the synthesised CRF microbeads was then analysed under various experimental conditions, and weed control efficacy determined under glasshouse conditions. Results revealed that adsorption of 2,4-D onto both organo-montmorillonites follows the pseudo-second-order kinetics model and is predominately controlled by the chemisorption process. However, multi-step mechanisms were detected in the adsorption on both organoclays, hence intra-particle diffusion is not the sole rate-limiting step for the adsorption process. Both organoclays followed the Elovich model, suggesting they have energetically heterogeneous surfaces. Herbicide-releasing behaviours of synthesised beads were investigated at various pH temperatures and ionic strengths under laboratory and glasshouse conditions. Furthermore, weed control efficacy of synthesised beads were investigated using pot studies under glasshouse condition. Desorption studies revealed that both synthesised microbeads have slow releasing behaviour at a wide range of pHs (5-9), temperatures (25-45 °C), and ionic strengths. The results also revealed that synthesised microbeads have excellent weed control efficacy on different broad-leaf weed species under glasshouse conditions.

Synthesised and modified zeolite for effective management of beryllium contaminants in aqueous media under different conditions.

The effective management of beryllium (Be) in solution is not well established. In this study, zeolite was synthesised from coal fly ash (CFA) and further modified to enhance Be sorption. Results indicated zeolite NaP1 was effectively synthesised, and cross-linked chitosan was grafted in/on the zeolite structure during modification. The Brunauer, Emmett, and Teller (BET) surface area substantially increased from 1.05 m2/g in CFA to 94.0 m2/g in the synthesised zeolite (SZ). Furthermore, the modified zeolite (MZ) showed improved functionality as a reactive site for Be sorption. A comparative sorption study revealed inferior sorption (11.3 %) and higher desorption (56.1 %) of Be using CFA than the sorption using SZ (93.0 % sorption, 2.9 % desorption) and MZ (93.0 % sorption, 1.5 % desorption). Consequently, SZ and MZ exhibited higher sorption efficacy than commercial zeolite (57.4 %) and other commercial sorbents. At an experimental pH of 5.5 [relevant to the pH of Little Forest Legacy Waste Site (LFLS) soil, a representative site for potential Be contamination], MZ showed higher sorption than SZ. The higher sorption in MZ resulted from its elevated ligand complexation [with nitrogen (N), phosphorous (P), and oxygen (O)] and some ion exchange (with Na+, -NH3+, and H+ ions) mechanisms. Moreover, increased sorption (up to 99 %) was observed using colloidal soil solution (CSS) collected from LFLS soil to simulate field conditions after extensive rainfall. Different environmental factors (e.g. pH, temperature, time, CSS, concentrations of sorbate, and sorbent) regulated Be sorption. The sorption mechanism was best described by the Langmuir model, and the pseudo-second-order kinetic model (R2 = 0.999). Moreover, the sorption reaction was spontaneous (ΔG = -Ve), enthalpically, and entropically influenced. Desorption hysteresis (ndesorption/nsorption < 1) suggested irreversible sorption, and the chemisorption mechanism of Be was confirmed by Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis.

Investigation of herbicide sorption-desorption using pristine and organoclays to explore the potential carriers for controlled release formulation.

Injudicious application of available commercial herbicide formulations leads to water, air and soil contamination, which adversely affect the environment, ecosystems and living organisms. Controlled release formulation (CRFs) could be an effective way to reduce the problems associated with commercially available herbicides. Organo-montmorillonites are prominent carrier materials for synthesising CRFs of commercial herbicides. Quaternary amine and organosilane functionalised organo-montmorillonite and pristine montmorillonite were used to investigate their potential as suitable carriers for CRFs in herbicide delivery systems. The experiment involved a batch adsorption process with successive dilution method. Results revealed that pristine montmorillonite is not a suitable carrier for CRFs of 2,4-D due to its low adsorption capacity and hydrophilic nature. Conversely, octadecylamine (ODA) and ODA-aminopropyltriethoxysilane (APTES) functionalised montmorillonite has better adsorption capacities. Adsorption of 2,4-D onto both organoclays is higher at pH.3 (232.58% for MMT1 and 161.29% for MMT2) compared to higher pH until pH.7 (49.75% for MMT1 and 68.49% for MMT2). Integrated structural characterisation studies confirmed the presence of 2,4-D on the layered organoclays. The Freundlich adsorption isotherm model fitted best to the experimental data, which revealed an energetically heterogeneous surface of the experimental organoclays, and adsorption which specifically involved chemisorption. The cumulative desorption percentages of adsorbed 2,4-D from MMT1(2,4-D loaded) and MMT2(2,4-D loaded) after seven desorption cycles were 65.53% and 51.45%, respectively. This outcome indicates: firstly, both organoclays are potential carrier materials for CRFs of 2,4-D; secondly, they have the ability to reduce the instantaneous release of 2,4-D immediately after application; and thirdly, eco-toxicity is greatly diminished.

Environmental chemistry response of beryllium to diverse soil-solution conditions at a waste disposal site.

This study evaluated how the variation in different sorption conditions of beryllium (Be) in soil-water systems (electrolytes; ionic strengths; competing, counter, and co-existing ions; concentrations of Be and soil; and temperature) affected Be's environmental behaviour. For this reason, potentially contaminated soil was collected from a legacy waste site near Sydney, Australia. The sorption-desorption plateau for Be was found at >12.5 g L-1 (soil/solution), considering higher sorption and limited desorption. Variable surface charges developed by different added ions (competing ions, counter ions, and co-existence of all ions) were not always correlated with Be sorption. However, effects of added ions in Be sorption (increased by counter ions and decreased by competing ions) primarily occurred at low pH, with no noticeable changes at pH > 6 due to the hydration and precipitation behaviour of Be at higher pH. Both laboratory data and modelling indicated the substantial effect of counter ions on increased sorption of Be. Relatively higher amounts of sorption under the co-existence of all added ions were suggested from synergistic actions. Sorption was favourable (KL > 0, and 0 < RL < 1) across all concentrations and temperatures at pH 5.5, and high retention (84-97%) occurred after four desorption cycles indicated specific sorption. The sorption process was exothermic (ΔH > -43 kJ mole-1), while desorption was endothermic (ΔH > +78.4 kJ mole-1). All sorption-desorption reactions were spontaneous (ΔG = -Ve), and executed without any structural deformation (ΔS = nearly zero) of soil particles. However, the effect of temperature on desorption was influenced by the concentrations of Be. Higher retention and different sorption-desorption parameters (Kd-desorption > Kd-sorption; Kf-desorption > Kf-sorption; ndesorption/nsorption < 1) indicate limited mobility of Be and the presence of desorption hysteresis in the studied soil under the experimental conditions.

Improving the Diagnosis of Endometrial Hyperplasia Using Computerized Analysis and Immunohistochemical Biomarkers.

Endometrial hyperplasia (EH) is a precursor lesion to endometrial carcinoma (EC). Risks for EC include genetic, hormonal and metabolic factors most notably those associated with obesity: rates are rising and there is concern that cases in pre-menopausal women may remain undetected. Making an accurate distinction between benign and pre-malignant disease is both a challenge for the pathologist and important to the gynecologist who wants to deliver the most appropriate care to meet the needs of the patient. Premalignant change may be recognized by histological changes of endometrial hyperplasia (which may occur with or without atypia) and endometrial intraepithelial neoplasia (EIN). In this study we created a tissue resource of EH samples diagnosed between 2004 and 2009 (n = 125) and used this to address key questions: 1. Are the EIN/WHO2014 diagnostic criteria able to consistently identify premalignant endometrium? 2. Can computer aided image analysis inform identification of EIN? 3. Can we improve diagnosis by incorporating analysis of protein expression using immunohistochemistry. Our findings confirmed the inclusion of EIN in diagnostic criteria resulted in a better agreement between expert pathologists compared with the previous WHO94 criteria used for the original diagnosis of our sample set. A computer model based on assessment of stromal:epithelial ratio appeared most accurate in classification of areas of tissue without EIN. From an extensive panel of putative endometrial protein tissue biomarkers a score based on assessment of HAND2, PTEN, and PAX2 was able to identify four clusters one of which appeared to be more likely to be benign. In summary, our study has highlighted new opportunities to improve diagnosis of pre-malignant disease in endometrium and provide a platform for further research on this important topic.

Role of beryllium in the environment: Insights from specific sorption and precipitation studies under different conditions.

In this study, we examined factors influencing the environmental behaviour of Be, specifically considering soils collected from a legacy radioactive waste disposal site near Sydney (Australia). The precipitation study showed the formation of Be(OH)2 (amorphous) from ICP standard solution, but a mixture of Be(OH)2 (alpha), Be(OH)2 (beta) and ternary Na/S-Be (ΙΙ)-OH(s) solid phase were formed from BeSO4 solutions. The precipitation of Be started at relatively lower pH at higher concentrations than at the lower Be concentration as indicated by both laboratory data and simulation. Across the pH range, the Be sorption curve was divided into three phases, these being pH 3-6, pH 6-10, and pH > 10, within which sorption of Be with soil was 9-97%, 90-97%, and 66-90%, respectively. Beryllium solubility was limited at pH > 7, but a sorption study with soil showed chemisorption under both acidic and alkaline pH (pH 5.5 and 8) conditions, which was confirmed by FTIR and XPS analysis. At pH 5.5 (specifically relevant to the study site), sorption of Be was 72-95%, in which 77% and 46% Be was respectively sorbed by separated fulvic and humic acid fractions. The irreversible chemisorption mechanism was controlled by SOM at higher pH, and by metal oxyhydroxides at lower pH. Both organic and inorganic components synergistically influence the specific chemisorption of Be at the intermediate pH 5.5 of field soil.

Evaluate the role of biochar during the organic waste composting process: A critical review.

Composting is very robust and efficient for the biodegradation of organic waste; however secondary pollutants, namely greenhouse gases (GHGs) and odorous emissions, are environmental concerns during this process. Biochar addition to compost has attracted the interest of scientists with a lot of publication in recent years because it has addressed this matter and enhanced the quality of compost mixture. This review aims to evaluate the role of biochar during organic waste composting and identify the gaps of knowledge in this field. Moreover, the research direction to fill knowledge gaps was proposed and highlighted. Results demonstrated the commonly referenced conditions during composting mixed biochar should be reached such as pH (6.5-7.5), moisture (50-60%), initial C/N ratio (20-25:1), biochar doses (1-20% w/w), improved oxygen content availability, enhanced the performance and humification, accelerating organic matter decomposition through faster microbial growth. Biochar significantly decreased GHGs and odorous emissions by adding a 5-10% dosage range due to its larger surface area and porosity. On the other hand, with high exchange capacity and interaction with organic matters, biochar enhanced the composting performance humification (e.g., formation humic and fulvic acid). Biochar could extend the thermophilic phase of composting, reduce the pH value, NH3 emission, and prevent nitrogen losses through positive effects to nitrifying bacteria. The surfaces of the biochar particles are partly attributed to the presence of functional groups such as Si-O-Si, OH, COOH, CO, C-O, N for high cation exchange capacity and adsorption. Adding biochars could decrease NH3 emissions in the highest range up to 98%, the removal efficiency of CH4 emissions has been reported with a wide range greater than 80%. Biochar could absorb volatile organic compounds (VOCs) more than 50% in the experiment based on distribution mechanisms and surface adsorption and efficient reduction in metal bioaccessibilities for Pb, Ni, Cu, Zn, As, Cr and Cd. By applicating biochar improved the compost maturity by promoting enzymatic activity and germination index (>80%). However, physico-chemical properties of biochar such as particle size, pore size, pore volume should be clarified and its influence on the composting process evaluated in further studies.

Effects of chelates (EDTA, EDDS, NTA) on phytoavailability of heavy metals (As, Cd, Cu, Pb, Zn) using ryegrass (Lolium multiflorum Lam.).

This paper summarises a study of the application of the synthetic chelate ethylenediaminetetraacetic acid (EDTA), and the natural chelates ethylenediamine-N,N'-disuccinic acid (EDDS) and nitrilotriacetate (NTA) to enhance ryegrass (Lolium multiflorum Lam.) uptake of the heavy metal(oid)s (HMs) (As, Cd, Cu, Pb and Zn) from contaminated soils in mining sites. The study compares the effects of these chelates (EDTA, EDDS and NTA) on the phytoavailability of HMs (As, Cd, Cu, Pb, Zn) using ryegrass (Lolium multiflorum Lam.) through the single addition and sequential addition methods. The results show that application of EDTA, EDDS and NTA significantly increases ryegrass (Lolium multiflorum Lam.)'s shoot uptake of some HMs when compared with no EDTA, EDDS or NTA application, particularly through sequential chelate treatment (EDTA 0.5:1+0.5:1; NTA 0.5:1+0.5:1; EDDS 0.5:1+0.5:1). EDTA 0.5:1+0.5:1 was more effective at increasing the concentration of Pb in shoots than were the other chelates (EDDS and NTA) and controls. Moreover, the concentrations of Zn in the shoots of ryegrass (Lolium multiflorum Lam.) in Hich Village significantly increased with the application of split dose (0.5:1+0.5:1). The plants displayed symptoms of toxicity including yellow and necrotic leaves at the end of the experiment. The selected chelates (EDTA, EDDS and NTA) led to a significant decrease in plant biomass (yield) 28 days after transfer with a maximum decrease in EDTA treatment (0.5:1+0.5:1) soils. This decrease was 3.43-fold in Ha Thuong, 3-fold in Hich Village and 1.59-fold in Trai Cau, respectively, relative to the control. HM concentration and dissolved organic carbon (DOC) in pore water provided an explanation for why fresh weight was significantly reduced with application of chelates in sequential dose (EDTA 0.5:1+0.5:1 and NTA 0.5:1+0.5:1).

Adsorption-Desorption Behavior of Arsenate Using Single and Binary Iron-Modified Biochars: Thermodynamics and Redox Transformation.

Arsenic (As) is a dangerous contaminant in drinking water which displays cogent health risks to humans. Effective clean-up approaches must be developed. However, the knowledge of adsorption-desorption behavior of As on modified biochars is limited. In this study, the adsorption-desorption behavior of arsenate (AsV) by single iron (Fe) and binary zirconium-iron (Zr-Fe)-modified biosolid biochars (BSBC) was investigated. For this purpose, BSBC was modified using Fe-chips (FeBSBC), Fe-salt (FeCl3BSBC), and Zr-Fe-salt (Zr-FeCl3BSBC) to determine the adsorption-desorption behavior of AsV using a range of techniques. X-ray photoelectron spectroscopy results revealed the partial reduction of pentavalent AsV to the more toxic trivalent AsIII form by FeCl3BSBC and Zr-FeCl3BSBC, which was not observed with FeBSBC. The Langmuir maximum AsV adsorption capacities were achieved as 27.4, 29.77, and 67.28 mg/g when treated with FeBSBC (at pH 5), FeCl3BSBC (at pH 5), and Zr-FeCl3BSBC (at pH 6), respectively, using 2 g/L biochar density and 22 ± 0.5 °C. Co-existing anions reduced the AsV removal efficiency in the order PO4 3- > CO3 2- > SO4 2- > Cl- > NO3 -, although no significant inhibitory effects were observed with cations like Na+, K+, Mg2+, Ca2+, and Al3+. The positive correlation of AsV adsorption capacity with temperature demonstrated that the endothermic process and the negative value of Gibbs free energy increased (-14.95 to -12.47 kJ/mol) with increasing temperature (277 to 313 K), indicating spontaneous reactions. Desorption and regeneration showed that recycled Fe-chips, Fe-salt, and Zr-Fe-salt-coated biochars can be utilized for the effective removal of AsV up to six-repeated cycles.

Beryllium in contaminated soils: Implication of beryllium bioaccessibility by different exposure pathways.

Inhalation exposure and beryllium (Be) toxicity are well-known, but research on bioaccessibility from soils via different exposure pathways is limited. This study examined soils from a legacy radioactive waste disposal site using in vitro ingestion (Solubility Bioaccessibility Research Consortium [SBRC], physiologically based extraction test [PBET], in vitro gastrointestinal [IVG]), inhalation (simulated epithelial lung fluid [SELF]) and dynamic two-stage bioaccessibility (TBAc) methods, as well as 0.43 M HNO3 extraction. The results showed, 70 ±â€¯4.8%, 56 ±â€¯16.8% and 58 ±â€¯5.7% of total Be were extracted (gastric phase [GP] + intestinal phase [IP]) in the SBRC, PBET, and IVG methods, respectively. Similar bioaccessibility of Be (~18%) in PBET-IP and SELF was due to chelating agents in the extractant. Moreover, TBAc-IP showed higher extraction (20.8 ±â€¯2.0%) in comparison with the single-phase (SBRC-IP) result (4.8 ±â€¯0.23%), suggesting increased Be bioaccessibility and toxicity in the gastrointestinal tract when the contamination derives from the inhalation route. The results suggested Be bioaccessibility depends on solution pH; time of extraction; soil reactive fractions (organic-inorganic); particle size, and the presence of chelating agents in the fluid. This study has significance for understanding Be bioaccessibility via different exposure routes and the application of risk-based management of Be-contaminated sites.

Desorption and Migration Behavior of Beryllium from Contaminated Soils: Insights for Risk-Based Management.

Factors influencing the desorption, distribution, and vertical migration behavior of Be in contaminated soils are not fully understood. This study examined the desorption and migration of Be in a soil profile from a legacy radioactive waste disposal site using different batch leaching [monofilled waste extraction procedure (MWEP); synthetic precipitation leaching procedure (SPLP); simulated acid rain solution (SARS); and toxicity characteristic leaching procedure] and sequential leaching [community bureau of reference (BCR)] methods for insights relevant to the application of risk-based management. The results showed that Be desorption was higher in the presence of organic than the inorganic leachate composition (MWEP < SPLP < SARS < TCLP < BCR first-step). The desorption followed three diffusion control mechanisms, which resulted in three desorption rate constant estimates of 157, 87.1, and 40.4 Be/kg.h0.5, and the estimated desorption maximum was 556 µg/kg. The desorption process was, spontaneous (ΔG > 0), enthalpically and entropically influenced. Increasing the incubation period and heat treatment resulted in a decrease of Be desorption and migration. The soil clay content and pH were the primary factors influencing Be desorption, and the results suggested that Be was desorbed from metal oxyhydroxides and surfaces of silicates (e.g., reactive surfaces of clay minerals), organic matters, and soil pores. Because of high K d values, the mobility of Be was limited, and no exceedances of ecological or human health risk index or guidelines were determined for the current contamination levels at the site. However, Be released from the waste trenches has the ongoing potential to increase Be concentration in the soil.

Arsenic bioaccessibility and fractionation in abandoned mine soils from selected sites in New South Wales, Australia and human health risk assessment.

Understanding the transport behaviour of arsenic (As) from soils to humans is critical when undertaking human health risk assessment and contamination control. This research examined As bioaccessibility in different As fractions and particle size fractions of As-enriched mine soils using different extractions. Bioaccessibility of As ranged from 0.24% to 32% for Solubility Bioaccessibility Research Consortium (SBRC) and Physiologically Based Extraction Test (PBET) methods, with extractable As (using 0.43 M HNO3) being 1.3-24.9%. The highest As bioaccessibility (19-32%) was consistently observed in the fine particle size fraction (< 53 µm) of all three extractions. Sequential extractions revealed that As fractions were mostly associated with crystalline (30-73%) and amorphous (9-59%) Fe/Al oxyhydroxides. The bioaccessibility of As in the gastric phase of SBRC and PBET methods highlighted a positive correlation (R2 = 0.83-0.88, p < 0.01) with exchangeable, surface and amorphous- bound As fractions, while the intestinal phase showed a strong positive correlation (R2 = 0.85-0.89, p < 0.01) with exchangeable and surface bound fractions. The study revealed that As bioaccessibility in soils can potentially be determined using the 0.43 M HNO3 extraction procedure. Health risk assessment confirmed that there was a strong increase in chronic daily intake, hazard quotient and cancer risk, with a reduction in particle size.

Antimonate sequestration from aqueous solution using zirconium, iron and zirconium-iron modified biochars.

Antimony (Sb) is increasingly being recognized as an important contaminant due to its various industrial applications and mining operations. Environmental remediation approaches for Sb are still lacking, as is the understanding of Sb environmental chemistry. In this study, biosolid biochar (BSBC) was produced and utilized to remove antimonate (Sb(V)) from aqueous solution. Zirconium (Zr), Zirconium-iron (Zr-Fe) and Fe-O coated BSBC were synthesized for enhancing Sb(V) sorption capacities of BSBC. The combined results of specific surface area, FTIR, SEM-EDS, TEM-EDS, and XPS confirmed that Zr and/or Zr-Fe were successfully coated onto BSBC. The effects of reaction time, pH, initial Sb(V) concentration, adsorbate doses, ionic strength, temperature, and the influence of major competitive co-existing anions and cations on the adsorption of Sb(V) were investigated. The maximum sorption capacity of Zr-O, Zr-Fe, Zr-FeCl3, Fe-O, and FeCl3 coated BSBC were 66.67, 98.04, 85.47, 39.68, and 31.54 mg/g respectively under acidic conditions. The XPS results revealed redox transformation of Sb(V) species to Sb(III) occurred under oxic conditions, demonstrating the biochar's ability to behave as an electron shuttle during sorption. The sorption study suggests that Zr-O and Zr-O-Fe coated BSBC could perform as favourable adsorbents for mitigating Sb(V) contaminated waters.

The influence of soil properties on sorption-desorption of beryllium at a low level radioactive legacy waste site.

This study examined the influence of soil physicochemical properties on the sorption, desorption and kinetics of beryllium (Be) uptake and release on soils from a legacy waste site in Australia. This information is needed to help explain the current distribution of Be at the site and evaluate potential future environmental risks. Sorption was determined by a batch study and key soil properties were assessed to explain Be retention. The soil was favourable for sorption of Be (up to 99%) due to organic content, negative surface charge, soil oxyhydroxides (Fe/Al/Mn-O/OH) and the porosity of the soil structure. Lesser sorption was observed in the presence of a background electrolyte (NaNO3). Sorption closely followed pseudo second order kinetics and was best described by the Langmuir model. FTIR analysis suggested that chemisorption was the predominant mechanism of Be sorption. Desorption was very low and best described by the Freundlich model. The low desorption reflected the high Kd (up to 6624 L/kg), and the presence of hysteresis suggested partially irreversible binding of Be with active surfaces of the soil matrix (minerals, SOM, oxyhydroxides of Fe/Al/Mn etc.). Intra-particle diffusion of Be and entrapment in the pores contribute to the irreversible binding. The sorption behaviour of Be helped to explain the relative immobility of Be at the site despite the significant quantities of Be disposed. Soil physicochemical properties were significant for Be sorption, through influencing both the uptake and desorption, and this demonstrates the implications of these measurements for evaluating potential future risks to the environment.

Reducing the radicality of surgery for vulvar cancer: are smaller margins safer?

INTRODUCTION: Vulvar cancer accounts for ~4% of all gynecological malignancies and the majority of tumors (>90%) are squamous cell (keratinizing, ~60% and warty/basaloid, ~30%). Surgical excision forms the foundation of treatment, with resection margin status being the single most influential factor when predicting clinical outcome. There has been a paradigm shift concerning surgical approaches and radicality when managing vulvar cancer within recent times, largely owing to a desire to preserve vulvar structure and function without compromising oncological outcome. As such the safety of the size of resection margin has been called into question. In this narrative review we consider the current literature on the safety of resection margins for vulvar cancer. EVIDENCE ACQUISITION: PubMed, Medline and the Cochrane Database were searched for original peer-reviewed primary and review articles, from January 2005 to January 2020. The following search terms were used vulvar cancer surgery, vulvar squamous cell carcinoma, excision margins, adjuvant radiation. EVIDENCE SYNTHESIS: A pathological tumor margin of <8 mm has been widely considered to indicate "close" margins. This measurement after fixation of the tumor is considered comparable to a surgical resection margin of around 1cm, following an estimated 20% tissue shrinkage after formalin fixation and a 1-2cm clinical surgical margin in order to achieve the 8 mm final pathological margin. CONCLUSIONS: A surgical resection margin of 2-3mm does not appear to be associated with a higher rate of local recurrence than the widely used limit of 8 mm. As such the traditional practice of re-excision or adjuvant radiotherapy based on "close" surgical margins alone needs to be closely evaluated, since the attendant morbidity associated with these procedures may not be outweighed by oncological benefit.

Removal of arsenate from contaminated waters by novel zirconium and zirconium-iron modified biochar.

A novel biochar metal oxide composite was synthesized for effective removal of arsenate (As(V)) from aqueous solution. The materials synthesized for As(V) removal was based on a biosolid-derived biochar (BSBC) impregnated with zirconium (Zr) and zirconium-iron (Zr-Fe). The synthesized materials were comprehensively characterized with a range of techniques including Brunauer-Emmett-Teller (BET-N2) surface area, zeta potential, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results confirmed that loading of Zr and Zr-Fe onto the biochar surface was successful. The influence of pH, biochar density, ionic strength, As(V) dose rate, major anions and cations on As(V) removal was also investigated. Under all pH and reaction conditions the Zr-Fe composite biochar removed the greatest As(V) from solution of the materials tested. The maximum sorption capacity reached 15.2 mg/g for pristine BSBC (pH 4.0), while modified Zr-BSBC and Zr-FeBSBC composites achieved 33.1 and 62.5 mg/g (pH 6), respectively. The thermodynamic parameters (Gibbs free energy, enthalpy, and entropy) suggested that the adsorption process is spontaneous and endothermic. The ZrBSBC and Zr-FeBSBC showed excellent reusability and stability over four cycles. Unmodified biochar resulted in partial reduction of As(V) under oxic conditions, whilst modified biochars did not influence the oxidation state of As. All results demonstrated that the Zr and Zr-Fe BSBC composites could perform as promising adsorbents for efficient arsenate removal from natural waters.

Are trainees working in obstetrics and gynecology confident and competent in the care of frail gynecological oncology patients?

INTRODUCTION: Older patients undergoing cancer surgery are at increased risk of post-operative complications, prolonged hospital stay, and mortality. Identification of frailty can help predict patients at high risk of peri-operative complications and allow a collaborative, multidisciplinary team approach to their care. A survey was conducted to assess the confidence and knowledge of trainees in obstetrics and gynecology regarding identification and management of peri-operative issues encountered in frail gynecological oncology patients. METHODS: A web-based survey was distributed via the Audit and Research in Gynaecological Oncology (ARGO) collaborative and UK Audit and Research Collaborative in Obstetrics and Gynaecology (UKARCOG) . The survey on the management of frail peri-operative patients was disseminated to doctors-in-training (trainees) working in obstetrics and gynecology in the United Kingdom (UK) and Ireland. Specialty (ST1-7), subspecialty, and general practice trainees, non-training grade doctors, and foundation year doctors currently working in obstetrics and gynecology were eligible. Consultants were excluded. Study data were collected using REDCAP software hosted at the University of Manchester. Responses were collected over a 6-week period between January and February 2020. RESULTS: Of the 666 trainees who participated, 67% (425/666) reported inadequate training in peri-operative management of frail patients. Validated frailty assessment tools were used by only 9% (59/638) of trainees and less than 1% (4/613) were able to correctly identify all the diagnostic features of frailty. Common misconceptions included the use of chronological age and gender in frailty assessments. The majority of trainees (76.5%, 448/586) correctly answered a series of questions relating to mental capacity; however, only 6% (36/606) were able to correctly identify all three diagnostic features of delirium. A total of 87% (495/571) of trainees supported closer collaboration with geriatricians and a multidisciplinary approach. CONCLUSIONS: Obstetrics and gynecology trainees reported inadequate training in the peri-operative care of frail gynecological oncology patients, and overwhelmingly favored input from geriatricians. Routine use of validated frailty assessment tools may aid diagnosis of frailty in the peri-operative setting. There is an unmet need for formal education in the management of frail surgical patients within the UK and Irish obstetrics and gynecology curriculum.

Comparison of in vitro models in a mice model and investigation of the changes in Pb speciation during Pb bioavailability assessments.

In this study, the predominant Pb minerals prior to and after Pb relative bioavailability (Pb-RBA) and Pb bioaccessibility (Pb-BAc) tests were identified using SEM (scanning electron microscopy), XANES (X-ray absorption near edge structure) and XRD (X-ray diffraction). The correlations between in vitro Pb-BAc (using the UBM (Unified BARGE Method) and RBALP (Relative BioAccessibility Leaching Procedure) models) and in vivo Pb-RBA (using endpoints of kidney and liver in an mice model) were determined. The results demonstrated that both RBALP and UBM (gastric phase) reliably indicate Pb-RBA (Pb-RBA). However, raising the solid:liquid ratio of the gastric phase of UBM is necessary to determine Pb-BAc if the soils contain total Pb >10,000 mg/kg. The comparison of Pb minerals prior to and after in vitro extractions demonstrated that the relatively soluble forms of Pb (PbSO4, PbO2 and MgO Pb) start to dissolve than other forms of Pb minerals, suggesting there was no difference in Pb2+ release between chemical-based (RBALP) and physiologically-based (UBM) models. The identification of the Pb minerals of Pb5(PO4)3Cl and organically-complexed Pb in mice excreta demonstrated that a portion of Pb2+ combined with food and humic acid to generate organically-complexed Pb in mice excreta, and that Pb5(PO4)3Cl is not bioavailable.