Limitations and insights regarding atmospheric mercury sampling using gold.

BACKGROUND: Atmospheric mercury (Hg) concentrations are quantified primarily through preconcentration on gold (Au) cartridges through amalgamation and subsequent thermal desorption into an atomic fluorescence spectrometry detector. This procedure has been used for decades, and is implemented in the industry-standard atmospheric Hg analyzer, the Tekran 2537. There is ongoing debate as to whether gaseous elemental mercury (Hg0) or total gaseous mercury (TGM, Hg0 + HgII) is measured using Au cartridges. The raw Hg signal processing algorithms for the Tekran 2537 analyzer have also been questioned. The objective of this work was to develop a better understanding of what forms of Hg are collected on gold cartridges through the use of permeation tube-based calibrators, that release known amounts of Hg0 and HgII. The potential differences between different Tekran analyzer models (i.e., 2537B versus 2537X) Hg signal processing algorithms, and Hg0 calibration methods were also investigated. RESULTS: Experiments were performed using Hg0 and HgII permeation calibrators. Validation tests showed that the HgII calibrator produced a reproducible and stable HgII permeation rate (2.2 ± 0.2 pg min-1). Results of HgII sampling and analysis using Au amalgamation showed the gold cartridges measured up to 75 % HgII, with the value at the beginning of the HgII measurement being much lower (as low as 10 %) due to HgII adsorption on analyzer surfaces and the Tekran particulate filter. Furthermore, thermal desorption of Hg from Au reduced only 80 % of HgII to Hg0, resulting in additional HgII that was not measured by the analyzer. By adding a thermolyzer upstream of the analyzer, 97 % of HgII was measured as Hg0. Additionally, Hg0 measurements using Tekran 2537 B and X models using a newly developed signal processing algorithm, different peak integration methods, and two Hg0 sources were compared. Results showed the 2537X model was not affected by the integration type, while the 2537B model was. Bell jar calibration based on the Dumarey equation resulted in 6 % ± 7 % (mean ± SD) underestimation of measured Hg0 concentrations compared to the calibration with a permeation calibrator. SIGNIFICANCE: Gold cartridges measured an atmospheric Hg fraction somewhere between Hg0 and TGM due to HgII adsorption and inefficient reduction of HgII to Hg0 during thermal desorption from Au. Since HgII in ambient air can be 25 % of total Hg, distinguishing between Hg0 and TGM is important. The use of a thermolyzer or a cation exchange membrane upstream of gold cartridges is recommended to enable TGM or Hg0 measurements, respectively. Observations showed that traceable multipoint calibrations of atmospheric Hg measurements are needed for Hg quantification, and that different Hg0 calibration methods can produce significantly different results for measured atmospheric Hg concentrations.

Revolutionizing urogynecology: Machine learning application with patient-centric technology: Promise, challenges, and future directions.

In an epoch where digital innovation is redefining the medical landscape, electronic health records (EHRs) stand out as a pivotal transformative force. Urogynecology, a discipline anchored in intricate patient histories and meticulous follow-ups, is on the brink of profound transformation due to these digital strides. While EHRs have unified patient data, challenges related to data privacy, interoperability, and access persist. In response, we present Pelvic Health Place (PHPlace) - a multilingual, patient-centric application. Purposefully designed to bolster patient engagement, PHPlace provides clinicians with essential pre-consultation insights, streamlines the consent process, vividly delineates surgical pathways, and assures comprehensive long-term monitoring. This platform also establishes a foundation for global data amalgamation, promising to invigorate research and potentially harness artificial intelligence (AI) capabilities. With AI integration, we anticipate a more tailored treatment approach and enriched patient education, signaling a pivotal shift in urogynecology and emphasizing the imperative for ongoing academic inquiry.

Is inadequate risk stratification diluting hazard ratio estimates in randomized clinical trials?

In randomized clinical trials, analyses of time-to-event data without risk stratification, or with stratification based on pre-selected factors revealed at the end of the trial to be at most weakly associated with risk, are quite common. We caution that such analyses are likely delivering hazard ratio estimates that unwittingly dilute the evidence of benefit for the test relative to the control treatment. To make our case, first, we use a hypothetical scenario to contrast risk-unstratified and risk-stratified hazard ratios. Thereafter, we draw attention to the previously published 5-step stratified testing and amalgamation routine (5-STAR) approach in which a pre-specified treatment-blinded algorithm is applied to survival times from the trial to partition patients into well-separated risk strata using baseline covariates determined to be jointly strongly prognostic for event risk. After treatment unblinding, a treatment comparison is done within each risk stratum and stratum-level results are averaged for overall inference. For illustration, we use 5-STAR to reanalyze data for the primary and key secondary time-to-event endpoints from three published cardiovascular outcomes trials. The results show that the 5-STAR estimate is typically smaller (i.e. more in favor of the test treatment) than the originally reported (traditional) estimate. This is not surprising because 5-STAR mitigates the presumed dilution bias in the traditional hazard ratio estimate caused by no or inadequate risk stratification, as evidenced by two detailed examples. Pre-selection of stratification factors at the trial design stage to achieve adequate risk stratification for the analysis will often be challenging. In such settings, an objective risk stratification approach such as 5-STAR, which is partly aligned with guidance from the US Food and Drug Administration on covariate-adjustment in clinical trials, is worthy of consideration.

Mercury cyanide complexes and their relevance as environmental contaminants.

This review addresses the formation and relevance of mercury cyanide complexes as environmental contaminants. Gold extraction is traditionally carried out through the process of mercury amalgamation (Hg) due to its simplicity and low cost. However, this process is inefficient, capturing only about 30% of the gold present in the processed material. Additionally, mercury is toxic, mobile, and capable of accumulating in aquatic ecosystems, leading to its prohibition in several countries. As an alternative, cyanidation has been widely used in gold extraction. However, the frequent combination of Hg amalgamation with cyanidation can result in the formation of mercury cyanide complexes, which can be released into local water bodies, potentially impacting human health and the environment. This article reviews the existing knowledge of these complexes and highlights the remaining gaps in understanding their environmental behavior. It also emphasizes the need to address concerns related to the formation of these complexes and seek solutions to minimize their negative impacts. Furthermore, the article highlights the lack of updates in the literature regarding the impacts of cyanidation and the limited availability of comprehensive information on the topic. It is essential to conduct updated research in this area to advance knowledge and promote safer and more responsible practices in the mining industry.

Compression-based Facies Modelling.

Simple object- or pixel-based facies models use facies proportions as the constraining input parameter to be honored in the output model. The resultant interconnectivity of the facies bodies is an unconstrained output property of the modelling, and if the objects being modelled are geometrically representative in three dimensions, commonly-available methods will produce well-connected facies when the model net:gross ratio exceeds about 30%. Geological processes have more degrees of freedom, and facies in high net:gross natural systems often have much lower connectivity than can be achieved by object-based or common implementations of pixel-based forward modelling. The compression method decouples facies proportion from facies connectivity in the modelling process and allows systems to be generated in which both are defined independently at input. The two-step method first generates a model with the correct connectivity but incorrect facies proportions using a conventional method, and then applies a geometrical transform to scale the model to the correct facies proportions while retaining the connectivity of the original model. The method, and underlying parameters, are described and illustrated using examples representative of low and high connectivity geological systems.

Vertical Stacking Statistics of Multi-facies Object-Based Models.

Equations describing facies proportions and amalgamation ratios are derived for randomly placed objects belonging to two or three foreground facies embedded in a background facies, as a function of the volume fractions and object thicknesses of independent facies models combined in a stratigraphically meaningful order. The equations are validated using one-dimensional continuum models. Evaluation of the equations reveals a simple relationship between an effective facies proportion and an effective amalgamation ratio, both measured as a function only of the facies in question and the background facies. This relationship provides a firm analytical basis for applying the compression algorithm to multi-facies object-based models. A set of two-dimensional cross-sectional models illustrates the approach, which allows models to be generated with realistic object stacking characteristics defined independently for each facies in a multi-facies object-based model.

Effects of chemical dispersants on feathers from Arctic seabirds.

Chemical dispersion is an oil spill response strategy where dispersants are sprayed onto the oil slick to enhance oil dispersion into the water. However, accidental application could expose seabirds to dispersants, thereby negatively affecting their plumage. To understand the possible impacts on seabirds, feathers from common eider (Somateria mollissima) and thick-billed murre (Uria lomvia) were exposed to different dosages of the dispersant Dasic Slickgone NS. For all exposure dosages the feathers increased in weight, and mostly for common eider. Analysing the feather microstructure, e.g., the Amalgamation Index, showed that larger damages were found on thick-billed murre than common eider. A no-sinking limit was established at 0.109 ml/m2. Relating this value to desktop simulations of potential sea-surface dosages in real-life situations, and to published accounts of response operations, showed that the limit is likely to be exceeded. Thus, our results show that chemical dispersants in realistic dosages could impact seabirds.

Highly efficient capture of mercury from complex water matrices by AlZn alloy reduction-amalgamation and in situ layered double hydroxide.

Mercury pollution is a critical, worldwide problem and the efficient, cost-effective removal of mercury from complex, contaminated water matrices in a wide pH range from strongly acidic to alkaline has been a challenge. Here, AlZn and AlFe alloys are investigated and a new process of synergistic reduction-amalgamation and in situ layered double hydroxide (SRA-iLDH) for highly efficient capture of aqueous Hg(II) is developed using AlZn alloys. The parameters include the pH values of 1-12, the Hg(II) concentrations of 10-1000 mg L-1, and the alloy's Zn concentrations of 20%, 50% and 70% and Fe concentrations of 10%, 20% and 50%. The initial rate of Hg(II) uptake by AlZn alloys decreases with increasing Zn concentration while the overall rate is not affected. Specifically, AlZn50 alloy removes >99.5% Hg(II) from 10 mg L-1 solutions at pH 1-12 in 5 min at a rate constant of 0.055 g mg-1 min-1 and achieves a capacity of 5000 mg g-1, being the highest value reported so far. The super-performance of AlZn alloy is attributed to multiple functions of chemical reduction, dual amalgamation, in situ LDH's surface complexation and adsorption, isomorphous substitution and intercalation. This study provides a simple and highly efficient approach for removing Hg(II) from complex water matrices.

Emerging mercury and methylmercury contamination from new artisanal and small-scale gold mining along the Nile Valley, Egypt.

The past decade witnessed the initiation and boom of the Artisanal and Small-scale Gold Mining (ASGM) activities in the hyper-arid southern Egypt. The ores are mined in the Eastern Desert and then transported to the densely populated farming communities in the Nile Valley, where the river provides the water resources needed for ore processing. In search for economic benefits, the poorly educated farmers with limited technical resources transformed their cultivated lands into ASGM operations, exposing themselves, their families, the residents, and the Nile ecosystems to several environmental and occupational health problems. Using integrated remote sensing, field, geochemical, and isotopic analyses, we report the first inventory of ASGM-related total mercury (THg) and methylmercury (MeHg) levels in tailings, amalgamation-tailing ponds, and surface and groundwater with emphasis on the Edfu city and its surroundings. The field and remote sensing-based mapping of ASGM activities reveals clustering around the Nile waterways and suggests interaction of Hg contamination sources with their surrounding receptors. Common ASGM practices include release of contaminated water from unlined amalgamation-tailing ponds into irrigation and drainage canals, and spreading of tailings over cultivated soils. In a short period (10 years), the released Hg contaminated multiple media, including the surface water, the shallow and deep aquifers, and possibly the soil, crops, and livestock. THg levels in amalgamation-tailing ponds (1200-8470 ng/L) are fourfold higher than US EPA and eightfold the WHO thresholds. The contaminated waters released from amalgamation-tailing ponds raised THg levels in surface water (irrigation canals: 50-100 ng/L; drainage canals: THg: > 200 ng/L) and groundwater (shallow and deep aquifers: 80-500 ng/L). Our findings highlight the need to extend the adopted approach to cover the entire length of the Nile River and its valley and the importance of conducting awareness campaigns to educate residents and health care providers about potential ASGM-related environmental and health hazards.

Specific colorimetric detection of methylmercury based on peroxidase-like activity regulation of carbon dots/Au NPs nanozyme.

Methylmercury (MeHg+) is one of the common organic species of mercury, and has much higher toxicity than inorganic mercury. Based on the selective enhancement of the activity of nanozyme (NA-CDs/AuNPs) by MeHg+, a novel colorimetric nanoprobe for MeHg+ assay is proposed. The noradrenaline-based carbon dots (NA-CDs) as the reducing agent was applied to prepare the NA-CDs/AuNPs. The formation of gold amalgamation (Au@HgNPs) between nanozyme and MeHg+ allows to simultaneously accelerate the electron transfer from Au and Hg to NA-CDs and the generation of radicals (i.e. ∙OH, ∙O2- and ∙CH3). The NA-CDs/AuNPs has an outstanding anti-interference performance even in the presence of different mercury. Further density functionality theory (DFT) calculations revealed that the formation of Au@HgNPs via MeHg+ contributes to the significantly lowered activation energy, resulting in the peroxidase-like activity generation and acceleration. This leads to rapid (10 min) and specific colorimetric detection of MeHg+ with the detection limit of 0.06 µg L-1. This introduces a novel method for simple and sensitive detection of MeHg+, giving a new horizon for the assay of organometallic compounds.

Local Multiset Dimension of Amalgamation Graphs.

Background: One of the topics of distance in graphs is the resolving set problem. Suppose the set W = { s 1, s 2, …, s k} ⊂ V ( G), the vertex representations of ∈ V ( G) is r m( x| W) = { d( x, s 1), d( x, s 2), …, d( x, s k)}, where d( x, s i) is the length of the shortest path of the vertex x and the vertex in W together with their multiplicity. The set W is called a local m-resolving set of graphs G if r m( v| W)≠ r m( u| W) for uv ∈ E( G). The local m-resolving set having minimum cardinality is called the local multiset basis and its cardinality is called the local multiset dimension of G, denoted by md l( G). Thus, if G has an infinite local multiset dimension and then we write mdlG=∞. Methods: This research is pure research with exploration design. There are several stages in this research, namely we choose the special graph which is operated by amalgamation and the set of vertices and edges of amalgamation of graphs; determine the set W ⊂ V ( G); determine the vertex representation of two adjacent vertices in G; and prove the theorem. Results: The results of this research are an upper bound of local multiset dimension of the amalgamation of graphs namely md l( Amal( G, v, m)) ≤ m. md l( G) and their exact value of local multiset dimension of some families of graphs namely md l( Amal( P n, v, m)) = 1, mdlAmalKnvm=∞, md l( Amal( W n, v, m)) = m. md l( W n), md l( Amal( F n, v, m)) = m. md l( F n) for d( v) = n, mdlAmalFnvm=m.n4. Conclusions: We have found the upper bound of a local multiset dimension. There are some graphs which attain the upper bound of local multiset dimension namely wheel graphs.

Estimating survival and adoption rates of dependent juveniles.

Population growth and fitness are typically most sensitive to adult survival in long-lived species, but variation in recruitment often explains most of the variation in fitness, as past selection has canalized adult survival. Estimating juvenile survival until age of independence has proven challenging, because marking individuals in this age class may directly affect survival. For Greater Sage-grouse, uniquely marking juveniles in the first days of life likely results in adverse effects to survival, detection of juveniles is not perfect, and females adopt juveniles from other parents. These challenges are encountered by researchers studying avian and mammalian species with similar life histories, yet methods do not exist that explicitly estimate all these components of the recruitment process. We propose a novel data collection method and demographic model to simultaneously estimate rates of detection, survival, and adoption of juvenile individuals. Using multiple cameras to film the beginning of juvenile activity on specific days, we obtained counts of juveniles associated with marked females. Increases of juveniles to broods provided information that enabled us to estimate rates of adoption that can be applied at the population level. Losses from broods informed apparent survival. These losses could be attributed to death, or they could be chicks that were adopted by other females. We found evidence that apparent survival of juveniles was influenced by localized weather patterns when chicks were young. Similarly, we found that young chicks were more susceptible to the adverse effect of attending females being flushed by an observer. Both of these patterns diminished quickly as chicks aged. We provide the first-ever estimates of interval-specific adoption rates. Our results suggest that researchers should be cautious when designing studies to estimate juvenile survival. More importantly, they provide insight into adoption, a behavior that has been known to exist for decades.

The partition dimension of the vertex amalgamation of some cycles.

Let G = ( V ( G ) , E ( G ) ) be a connected, finite, simple, and undirected graph. The distance between two vertices u , w ∈ V ( G ) , denoted by d ( u , w ) , is the shortest length of ( u , w ) -path in G. The distance between a vertex v ∈ V ( G ) is defined as min ⁡ { d ( v , x ) : x ∈ S } where S ⊂ V ( G ) , denoted by d ( v , S ) . For an ordered partition Π = { S 1 , S 2 , … , S k } of the vertices of a graph G, the partition representation of a vertex v ∈ V ( G ) with respect to Π is defined as the k-vektor r ( v | Π ) = ( d ( v , S 1 ) , d ( v , S 1 ) , … , d ( v , S 1 ) . The partition set Π is called a resolving partition of G, if r ( u | Π ) ≠ r ( v | Π ) , for all u ≠ v , u , v ∈ V ( G ) . The partition dimension of G is the minimum number of sets in any resolving partition of G. In this paper we study the partition dimension of the vertex amalgamation of some cycles. Specifically, we present the vertex amalgamation of m copies of the cycle C n at a fixed vertex v ∈ V ( C n ) , for n ≥ 6 and k 2 - 3 k + 4 2 ≤ m ≤ k 2 - k 2 , k ≥ 3 .

Simple and sensitive method for the determination of methylmercury in hair using thin-layer chromatography with thermal decomposition gold amalgamation atomic absorption spectrophotometry.

An improved method is described for the determination of methylmercury (MeHg) in human hair that is based on thin-layer chromatography and thermal decomposition gold amalgamation atomic absorption spectrophotometry. The dithizone extraction and application procedure of this technique were optimized, thus improving its sensitivity and robustness and enabling the use of less toxic solvents than other approaches. The limit of detection was 0.18 ng MeHg (as Hg), corresponding to 0.018 mg MeHg kg-1 of hair relative to a 10 mg sample. This method is appropriate for detecting MeHg in hair at the approximate reference dose level established by the United States Environmental Protection Agency.

Investigation of Radiolabeling Efficacy by Enhancement of the Chemical form of no Carrier Added 177Lu Isolated by Electro Amalgamation Process.

BACKGROUND: Due to the suitable nuclear decay characteristics, 177Lu is an attractive radionuclide for various therapeutic applications. The non-carrier added form of177Lu has drawn much attention because of its high specific activity needed in radiolabeling studies. There have been several separation methods for NCA177Lu production. OBJECTIVES: Among the various separation methods, the electro-amalgamation separation method has got a large potential for large scale production. Li presence is a significant problem in this separation method, which seriously affects the radiolabeling efficiency. METHODS: In this study, Li was separated from the final product of electro-amalgamation separation by adding an ion-exchange chromatography column to the separation process. RESULTS: NCA 177Lu was obtained by 84.09% ELM separation yield, 99.9% radionuclide purity and, 65 Ci/g specific activity. Then, 177Lu (177LuCl3 chemical form) was separated from Li using the ion exchange chromatography method by a separation yield of 94%. The obtained results of the radiolabeling efficacy studies showed that the radiochemical purity and radio-complex stability were significantly increased by separating NCA 177Lu from Li. CONCLUSION: This new separation setup consisting of two steps allows using 177Lu of such a favorable quality for labeling studies.

A capillary-based SERS sensor for ultrasensitive and selective detection of Hg2+ by amalgamation with Au@4-MBA@Ag core-shell nanoparticles.

A capillary-based SERS sensor was fabricated for ultrasensitive and selective detection of Hg2+ in water. Au@Ag core-shell NPs embedded with 4-mercaptobenzoic acid (4-MBA) (Au@4-MBA@Ag) were prepared by a seed growth method and fixed on the inner wall of the glass capillary to obtain the sensor. Owing to the amalgamation between Ag and Hg, the capillary-based SERS sensor can specifically recognize the reduced Hg2+ without any recognition element, and the resulted Ag/Hg amalgam can weaken the SERS activity of Ag shell; thus, the SERS intensity of the embedded 4-MBA at 1075 cm-1 gradually decreased with the increase of Hg2+ concentration. Under the optimum condition, the fabricated sensor can sensitively determine Hg2+ in water with a limit of detection (LOD) as low as 0.03 nM. The capillary-based SERS sensor offers the advantages of simple preparation, superior stability, and high selectivity, which is promising for rapid and on-site detection of Hg2+ in water combined with a portable Raman device.

Evaluation of the Total Mercury Weight Exposure Distribution Using Tree Bark Analysis in an Artisanal and Small-Scale Gold Mining Area, North Gorontalo Regency, Gorontalo Province, Indonesia.

It is well known that atmospheric mercury (Hg) contaminates air, water, soil, and living organisms, including trees. Therefore, tree bark can be used for the environmental assessment of atmospheric contamination because it absorbs heavy metals. This study aimed to establish a new biomonitoring for the assessment of atmospheric Hg pollution. Reporting on atmospheric Hg contamination in an artisanal and small-scale gold mining (ASGM) area in North Gorontalo, Indonesia, we calculated the total weight of Hg (THg) and quantitatively measured the concentrations of Hg in the tree bark of Mangifera indica, Syzygium aromaticum, Terminalia catappa, and Lansium domesticum. The THg of Hg in the M. indica tree bark samples ranged from not detected (ND) to 74.6 µg dry weight (DW) per sample. The total Hg in the tree bark of S. aromaticum, T. catappa, and L. domesticum ranged from ND to 156.8, ND to 180, and ND to 63.4 µg DW, respectively. We concluded that topography significantly influences the accumulation of Hg together with local weather conditions. A mapped distribution of the THg suggested that the distribution of THg in the tree bark was not affected by the distance to the amalgamation site. Therefore, tree bark can be used as biomonitoring of atmospheric Hg contamination for the assessment of ASGM areas.

Case study research in the social sciences.

In this paper, we offer an introduction to case study research in the social sciences. We begin with a discussion of the definition of case study research. Next, we point to various purposes that case study research may serve in the social sciences and then turn to outline the main philosophical issues raised by case study research. Finally, we briefly present the papers in this special issue.

Mercury isotopic signatures of tailings from artisanal and small-scale gold mining (ASGM) in southwestern Ecuador.

Artisanal and small-scale gold mining (ASGM) is currently one of the largest anthropogenic sources of mercury (Hg) to the atmosphere and a significant source to downstream terrestrial aquatic systems. Given the potential toxicity of Hg when it is released to aquatic ecosystems, both scientific and regulatory communities have interest in the development of tools and methods for understanding the fate and transport of Hg in the environment. Although Hg isotopes are applied extensively to trace other anthropogenic point sources of Hg in aquatic ecosystems, few studies have used isotopic analyses to investigate the downstream impacts of ASGM. Furthermore, these studies are currently limited by relatively sparse Hg isotopic analyses on ASGM materials. In this study, ASGM samples from Portovelo-Zaruma (Ecuador), representing various stages of the processing of low-grade gold-bearing ores, were analyzed for Hg concentrations and stable isotope ratios. These data were used to assess the isotopic variability of the ASGM endmember and confirm the results of prior isotopic analyses of ASGM materials and downstream sediments from Portovelo-Zaruma. While the Hg concentrations of the ASGM samples varied significantly, isotopic analyses revealed a limited range of signatures that was characterized by relatively heavy mass-dependent fractionation (MDF) with little to no significant mass-independent fractionation (MIF). The signatures of ASGM samples analyzed in this study matched well with previously reported ASGM samples from Portovelo-Zaruma as well as downstream sediments (for up to 120 km). Furthermore, the overall Hg isotopic compositions of potential ASGM endmembers are distinct from typical compositions observed in freshwater ecosystems (e.g., from soil erosion, atmospheric deposition), allowing Hg isotopes to be a powerful tool in tracing downstream Hg contamination from ASGM.

Syntactic characterizations of classes of first-order structures in mathematical fuzzy logic.

This paper is a contribution to graded model theory, in the context of mathematical fuzzy logic. We study characterizations of classes of graded structures in terms of the syntactic form of their first-order axiomatization. We focus on classes given by universal and universal-existential sentences. In particular, we prove two amalgamation results using the technique of diagrams in the setting of structures valued on a finite MTL-algebra, from which analogues of the Los-Tarski and the Chang-Los-Suszko preservation theorems follow.