Field method for preservation of total mercury in waters, including those associated with artisanal scale gold mining.

Analysis of mercury (Hg) in natural water samples has routinely been impractical in many environments, for example, artisanal and small-scale gold mines (ASGM), where difficult conditions make monitoring of harmful elements and chemicals used in the processes highly challenging. Current sampling methods require the use of hazardous or expensive materials, and so difficulties in sample collection and transport are elevated. To solve this problem, a solid-phase extraction-based method was developed for the sampling and preservation of dissolved Hg in natural water samples, particularly those found around ASGM sites. Recoveries of 85% ± 10% total Hg were obtained during 4 weeks of storage in refrigerated (4 °C, dark) and unrefrigerated (16 °C, dark) conditions, and from a representative river water spiked to 1 µg L-1 Hg2+, 94% ± 1% Hg recovery was obtained. Solid-phase extraction loading flow rates were tested at 2, 5, and 10 mL min-1 with no breakthrough of Hg, and sorbent stability showed no breakthrough of Hg up to 2 weeks after functionalisation. The method was deployed across five artisanal gold mines in Kakamega gold belt, Kenya, to assess Hg concentrations in mine shaft water, ore washing ponds, and river and stream water, including drinking water sources. In all waters, Hg concentrations were below the WHO guideline limit value of 6 µg L-1, but drinking water sources contained trace concentrations of up to 0.35 µg L-1 total Hg, which may result in negative health effects from long-term exposure. The SPE method developed and deployed here is a robust sampling method that can therefore be applied in future Hg monitoring, toxicology, and environmental work to provide improved data that is representative of total dissolved Hg in water samples.

Public health assessment of Kenyan ASGM communities using multi-element biomonitoring, dietary and environmental evaluation.

The Kakamega gold belt's natural geological enrichment and artisanal and small-scale gold mining (ASGM) have resulted in food and environmental pollution, human exposure, and subsequent risks to health. This study aimed to characterise exposure pathways and risks among ASGM communities. Human hair, nails, urine, water, and staple food crops were collected and analysed from 144 ASGM miners and 25 people from the ASGM associated communities. Exposure to PHEs was predominantly via drinking water from mine shafts, springs and shallow-wells (for As>Pb>Cr>Al), with up to 366 µg L-1 arsenic measured in shaft waters consumed by miners. Additional exposure was via consumption of locally grown crops (for As>Ni>Pb>Cr>Cd>Hg>Al) besides inhalation of Hg vapour and dust, and direct dermal contact with Hg. Urinary elemental concentrations for both ASGM workers and wider ASGM communities were in nearly all cases above bioequivalents and reference upper thresholds for As, Cr, Hg, Ni, Pb and Sb, with median concentrations of 12.3, 0.4, 1.6, 5.1, 0.7 and 0.15 µg L-1, respectively. Urinary As concentrations showed a strong positive correlation (0.958) with As in drinking water. This study highlighted the importance of a multidisciplinary approach in integrating environmental, dietary, and public health investigations to better characterise the hazards and risks associated with ASGM and better understand the trade-offs associated with ASGM activities relating to public health and environmental sustainability. Further research is crucial, and study results have been shared with Public Health and Environmental authorities to inform mitigation efforts.

Identifying Sources of Lead Exposure for Children in the Republic of Georgia, with Lead Isotope Ratios.

In the Republic of Georgia, a 2018 national survey estimated that more than 40% of children aged 2-7 years had a blood lead concentration (BLC) of more than 5 µg/dL. The objective of this study was to document the feasibility of employing lead isotope ratios (LIRs) to identify and rank the Pb (lead) exposure sources most relevant to children across Georgia. A cross-sectional survey between November 2019 and February 2020 of 36 children previously identified as having BLCs > 5 µg/dL from seven regions of Georgia involved the collection of blood and 528 environmental samples, a questionnaire on behaviours and potential exposures. The LIRs in blood and environmental samples were analysed in individual children and across the whole group to ascertain clustering. A fitted statistical mixed-effect model to LIR data first found that the blood samples clustered with spices, tea, and paint, then, further isotopically distinct from blood were sand, dust, and soil, and lastly, milk, toys, pens, flour, and water. Analysis of the LIRs provided an indication and ranking of the importance of Pb environmental sources as explanatory factors of BLCs across the group of children. The findings support the deployment of interventions aimed at managing the priority sources of exposure in this population.

Pediatric Experience and Outcomes from the First Single-Vault Compact Proton Therapy Center.

The first single-vault compact proton therapy center opened in 2013, utilizing a gantry-mounted synchrocylotron. The center was placed within a large academic radiation oncology department with a high priority for pediatric cancer care. Here we performed a retrospective study of pediatric (≤21 years) patients treated with proton therapy at our institution between 2013-2022. Patient, tumor, and treatment characteristics were obtained including race, socioeconomic status, insurance type, distance travelled, need for anesthesia, and outside referrals for proton therapy. In total, 250 pediatric patients were treated with proton therapy comprising 18% of our proton patient volume. Median follow-up was 3.1 years, 38.4% were female and 83% were white. The majority of cases were CNS (69.6%) and a large number of patients (80/250, 32%) required craniospinal irradiation. Anesthesia was required for 39.6% of patients. Average distance travelled for treatment was 111 miles and 23% of patients were referred from outside institutions for proton therapy. Insurance type was private/commercial for 61.2% followed by Medicaid for 32%. We found that 23% of patients lived in census tracts with >25% of people living below the national poverty line. Overall survival at 3 years was excellent at 83.7% with better outcomes for CNS patients compared to non-CNS patients. There were no cases of secondary malignancy at this early time point. As the world's first compact proton therapy center, we found that proton therapy increased our pediatric volume and provided proton therapy to a diverse group of children in our region. These data highlight some of the expected patient and tumor characteristics and necessary resources for providing pediatric proton beam therapy.

Optimisation of plutonium separations using TEVA cartridges and ICP-MS/MS analysis for applicability to large-scale studies in tropical soils.

The analysis of plutonium (Pu) in soil samples can inform the understanding of soil erosion processes globally. However, there are specific challenges associated for analysis in tropical soils and so an optimal analytical methodology ensuring best sensitivity is critical. This method aimed to demonstrate the feasibility of sample preparation and analysis of Pu isotopes in African soils, considering the environmental and cost implications applicable to low-resource laboratories. The separation procedure builds upon previous work using TEVA columns, further demonstrating their usefulness for the reduction of uranium (U) interference in ICP-MS analysis with enhanced selectivity for Pu. Here several steps were optimised to enhance Pu recovery, reducing method blank concentration, and improving the separation efficiency through the determination of the elution profiles of U and Pu. The elimination of the complexing agent in the eluent, increased the spike recovery by improving matrix tolerance of the plasma, and simplified the separation procedure, improving throughput by 20%. The subsequent method was validated through the analysis of Certified Reference Material IAEA-384, where high accuracy and improved precision of measurement were demonstrated (measured value 114 ± 12 versus certified value 108 ± 13 Bq kg-1). Optimisation of the column separation, along with the analysis of the samples using O2 gas in ICP-MS/MS mode to mass shift Pu isotopes away from interfering molecular U ions provided a simple, robust, and cost-effective method with low achievable method detection limits of 0.18 pg kg-1 239+240Pu, applicable to the detection of ultra-trace fallout Pu in African soils.

Artisanal gold mining in Kakamega and Vihiga counties, Kenya: potential human exposure and health risk.

Artisanal and small-scale gold mining (ASGM) represents 20% of gold supply and 90% of gold mining workforce globally, which operates in highly informal setups. Pollutants from mined ores and chemicals introduced during gold processing pose occupational and inadvertent health risks to the extent that has not been well elucidated in Africa. Trace and major elements were analysed using inductively coupled plasma mass spectrometry in soil, sediment and water samples from 19 ASGM villages in Kakamega and Vihiga counties. Associated health risks for residents and ASGM workers were assessed. This paper focuses on As, Cd, Cr, Hg, Ni and Pb for which 96% of soil samples from mining and ore processing sites had As concentrations up to 7937 times higher than the US EPA 12 mg kg-1 standard for residential soils. Soil Cr, Hg and Ni concentrations in 98%, 49% and 68% of the samples exceeded respective USEPA and CCME standards, with 1-72% bioaccessibility. Twenty-five percentage of community drinking water sources were higher than the WHO 10 µg L-1 drinking water guideline. Pollution indices indicated significant enrichment and pollution of soils, sediment and water in decreasing order of As > Cr > Hg > Ni > Pb > Cd. The study revealed increased risks of non-cancer health effects (98.6) and cancer in adults (4.93 × 10-2) and children (1.75 × 10-1). The findings will help environment managers and public health authorities better understand the potential health risks in ASGM and support evidence-based interventions in ASGM processes, industrial hygiene and formulation of public health policy to protect residents and ASGM workers' health in Kenya.

A new hazard assessment workflow to assess soil contamination from large and artisanal scale gold mining.

Gold mining activities are undertaken both at large and artisanal scale, often resulting in serious 'collateral' environmental issues, including environmental pollution and hazard to human and ecosystem health. Furthermore, some of these activities are poorly regulated, which can produce long-lasting damage to the environment and local livelihoods. The aim of this study was to identify a new workflow model to discriminate anthropogenic versus geogenic enrichment in soils of gold mining regions. The Kedougou region (Senegal, West Africa) was used as a case study. Ninety-four soil samples (76 topsoils and 18 bottom soils) were collected over an area of 6,742 km2 and analysed for 53 chemical elements. Robust spatial mapping, compositional and geostatistical models were employed to evaluate sources and elemental footprint associated with geology and mining activities. Multivariate approaches highlighted anomalies in arsenic (As) and mercury (Hg) distribution in several areas. However, further interpretation with enrichment factor (EFs) and index of geoaccumulation (IGeo) emphasised high contamination levels in areas approximately coinciding with the ones where artisanal and small scale mining (ASGM) activities occur, and robust compositional contamination index (RCCI) isolated potentially harmful elements (PHE) contamination levels in very specific areas of the Kedougou mining region. The study underlined the importance of complementary approaches to identify anomalies and, more significantly, contamination by hazardous material. In particular, the analyses helped to identify discrete areas that would require to be surveyed in more detail to allow a comprehensive and thorough risk assessment, to investigate potential impacts to both human and ecosystem health.

The present and potential future of aqueous mercury preservation: a review.

Mercury is considered to be one of the most toxic elements to humans. Due to pollution from industry and artisanal gold mining, mercury species are present globally in waters used for agriculture, aquaculture, and drinking water. This review summarises methods reported for preserving mercury species in water samples and highlights the associated hazards and issues with each. This includes the handling of acids in an uncontrolled environment, breakage of sample containers, and the collection and transport of sample volumes in excess of 1 L, all of which pose difficulties for both in situ collection and transportation. Literature related to aqueous mercury preservation from 2000-2021 was reviewed, as well as any commonly cited and relevant references. Amongst others, solid-phase extraction techniques were explored for preservation and preconcentration of total and speciated mercury in water samples. Additionally, the potential as a safe, in situ preservation and storage method for mercury species were summarised. The review highlighted that the stability of mercury is increased when adsorbed on a solid-phase and therefore the metal and its species can be preserved without the need for hazardous reagents or materials in the field. The mercury species can then be eluted upon return to a laboratory, where sensitive analytical detection and speciation methods can be better applied. Developments in solid phase extraction as a preservation method for unstable metals such as mercury will improve the quality of representative environmental data, and further improve toxicology and environmental monitoring studies.

Method development to characterise elephant tail hairs by LA-ICP-MS to reflect changes in elemental chemistry.

This paper evaluated analytical methods used to generate time-series data from elephant tail hairs, which can be used to reflect changing exposure to environmental geochemistry. Elephant tail hairs were analysed by three methods sequentially, each providing data to inform subsequent analysis. Scanning Electron Microscopy (SEM) and X-ray Microanalysis visually showed the structure of the hair, specific structures such as tubules, and the mineral crusting around the edge of the hair, informing targeting of subsequent analysis by Laser Ablation-Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LA-ICP-MS generated time-series data which informed sectioning of the tail hairs for subsequent quantitative analysis for potentially toxic elements and micronutrients using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) of dissolved tail hairs. This novel approach to characterise the tail hair enabled time-series analysis to reflect changes in environmental exposure which may result from seasonal or geochemical spatial variation and could inform elephant movement patterns. The seasonal change between wet and dry seasons was reflected down the length of the hair. Correlations were seen between LA-ICP-MS data and ICP-MS data in several elements including Mg, P, Ca, Fe, Na, Mn and U. This study provided time-series data for the analysis of elephant tail hairs by evaluating analytical challenges to obtaining quantitative data, such as improving protocols to ensure removal of extraneous material, determining where to section the tail hairs to best reflect environmental changes/exposure and ensuring representative analyses. A protocol was established to determine mineral status across a 12-18 month time period utilizing single elephant tail hairs.

Arsenic doping and diffusion in CdTe: a DFT study of bulk and grain boundaries.

The doping of CdTe with As is a method which is thought to increase cell efficiency by increasing electron hole concentrations. This doping relies on the diffusion of As through CdTe resulting in AsTesubstitution. The potential effectiveness of this is considered through kinetic and electronic properties calculations in both bulk and Σ3 and Σ9 grain boundaries using Density Functional Theory. In bulk zinc-blende CdTe, isolated As diffuses with barriers <0.5 eV and with similar barriers through wurtzite structured CdTe, generated by stacking faults, suggesting that As will not be trapped at the stacking faults and hence the transport of isolated As will be unhindered in bulk CdTe. Substitutional arsenic in bulk CdTe has little effect on the band gap except when it is positively charged in the AX-centre position or occurring as a di-interstitial. However in contrast to the case of chlorine, arsenic present in the grain boundaries introduces defect states into the band gap. This suggests that a doping strategy whereby the grain boundaries are first saturated with chlorine, before single arsenic atoms are introduced, might be more beneficial.

The Use of Pb Isotope Ratios to Determine Environmental Sources of High Blood Pb Concentrations in Children: A Feasibility Study in Georgia.

The incidence of lead (Pb) poisoning in children in Georgia has been identified as a major health concern, with a recent national survey identifying that 41% of children aged 2-7 years had blood lead concentrations (BLCs) greater than the blood lead reference value (BLRV) of ≥5 µg dL-1. This study collected samples of blood, spices, paint, soil, dust, flour, tea, toys, milk, and water from 36 households in Georgia where a child had previously been identified as having a BLC > BLRV. The Pb concentrations of these samples were determined and compared to Georgian reference values. Samples from 3 households were analysed for their Pb isotope composition. The Pb isotope composition of the environmental and blood samples were compared to identify the most likely source(s) of Pb exposure. This approach identified that some spice and dust samples were the likely sources of Pb in the blood in these cases. Importantly, some soil, paint, and dust sources with high Pb concentrations could be discounted as contributing to blood Pb based on their distinct isotope composition. The data presented demonstrate the significant contribution that Pb surveillance and Pb isotope ratio analyses can make to managing Pb exposure in regions where high BLCs are identified.

In flux: Annual transport and deposition of suspended heavy metals and trace elements in the urbanised, tropical Red River Delta, Vietnam.

Due to the depositional environment, river deltas are said to act as filters and sinks for pollutants. However, many deltas are also densely populated and rapidly urbanizing, creating new and increased sources of pollutants. These sources pose the risk of tipping these environments from pollution sinks to sources, to the world's oceans. We provide detailed seasonal and annual assessments of metal contaminants in riverine suspended particulate matter (SPM) across the densely populated Red River Delta (RRD), Vietnam. The global contributions of elements from the RRD are all <0.2% with many elemental fluxes <0.01%, suggesting the RRD is not a major source of elemental pollution to the ocean. However, 'hotspots' of metal pollution due to human activity and the impacts of tropical storm Son Tinh (July 2018) exceed both national level regulations and international measures of toxicity (e.g. enrichment factors). There is widespread 'extreme pollution' of Cd (enrichment factor >40) and concentrations of As higher than national regulation limits (>17 mg/Kg) at all sites other than one upstream, agricultural-dominated tributary in the dry season. These 'hotspots' are characterised by high inputs of organic matter (e.g. manure fertiliser and urban wastewater), which influences elemental mobility in the particulate and dissolved phases, and are potentially significant sources of pollution downstream. In addition, in the marine and fresh water mixing zone, salinity effects metal complexation with organic matter increasing metals in the particulate phase. Our calculations indicate that the delta is currently acting as a pollutant sink (as determined by high levels of pollutant deposition ∼50%). However, increased in-washing of pollutants and future projected increases in monsoon intensity, saline intrusion, and human activity could shift the delta to become a source of toxic metals. We show the importance of monitoring environmental parameters (primarily dissolved organic matter and salinity) in the RRD to assess the risk of transport and accumulation of toxic metals in the delta sediments, which can lead to net-increases in anthropogenic pollution in the coastal zone and the incorporation of toxic elements in the food chain.

Integrated visible-light liquid-crystal-based phase modulators.

In this work, an integrated liquid-crystal-based phase modulator operating at visible wavelengths was developed and experimentally demonstrated. A visible-light silicon-nitride-based 300-mm-wafer foundry platform and a liquid-crystal integration process were developed to leverage the birefringence of liquid crystal to actively tune the effective index of a section of silicon-nitride waveguide and induce a phase shift over its length. The device was experimentally shown to achieve a 41π phase shift within 4.8 Vpp for a 500-µm-long modulator, which means that a 2π phase shifter would need to be only 24.4 µm long. This device is a compact and low-power solution to the challenge of integrated phase modulation in silicon nitride and paves the way for future low-power small-form-factor integrated systems at visible wavelengths.

Attic dust: an archive of historical air contamination of the urban environment and potential hazard to health?

A comprehensive study of attic dust in an urban area is presented. Its entire life cycle, from determining historical emission sources to recognising the processes that take place in attic dust and its potential to impact human health is discussed. Its chemical composition and morphological characteristics of individual solid particles reflect past anthropogenic activities. High levels of Be-Cd-Cu-Sb-Sn-Pb-Te-Zn and occurrence of Cu-Zn shavings are typical for an industrial zone characterised by a foundry and a battery factory. High levels of Co-Fe-Mo-Ni-W-Ba-Cr-Mg-Mn-Nb-Ti and occurrence of various solid Fe-oxides, particularly spherical particles, were identified in another industrial zone, which was dominated by the automotive and metal-processing industries. Emissions from coal combustion affected the distribution of S-Se-Hg-Tl-As-Ag-U. The predominant mineral in attic dust is gypsum, which was presumably formed in situ by the reaction of carbonate dust particles and atmospheric SO2 gas. The high oral bioaccessibility of As-Cd-Cu-Pb-Zn in the gastric phase and high bioaccessibility of As-Cu-Cd-Ni in the gastrointestinal phase were identified. Determined characteristics of attic dust and identified possibilities of prolonged human exposure to it indicate that attic dust should be treated as an excellent proxy for historical air contamination as well as a potentially hazardous material for human health.

Evaluating spatio-temporal soil erosion dynamics in the Winam Gulf catchment, Kenya for enhanced decision making in the land-lake interface.

Soil erosion accelerated by poor agricultural practices, land degradation, deprived infrastructure development and other anthropogenic activities has important implications for nutrient cycling, land and lake productivity, loss of livelihoods and ecosystem services, as well as socioeconomic disruption. Enhanced knowledge of dynamic factors influencing soil erosion is critical for policymakers engaged in land use decision-making. This study presents the first spatio-temporal assessment of soil erosion risk modelling in the Winam Gulf, Kenya using the Revised Universal Soil Loss Equation (RUSLE) within a geospatial framework at a monthly resolution between January 2017 and June 2020. Dynamic rainfall erosivity and land cover management factors were derived from existing datasets to determine their effect on average monthly soil loss by water erosion. By assessing soil erosion rates with enhanced temporal resolution, it is possible to provide greater knowledge regarding months that are particularly susceptible to soil erosion and can better inform future strategies for targeted mitigation measures. Whilst the pseudo monthly average soil loss was calculated (0.80 t ha-1 month-1), the application of this value would lead to misrepresentation of monthly soil loss throughout the year. Our results indicate that the highest erosion rates occur between February and April (average 0.95 t ha-1 month-1). In contrast, between May and August, there is a significantly reduced risk (average 0.72 t ha-1 month-1) due to the low rainfall erosivity and increased vegetation cover as a result of the long rainy season. The mean annual gross soil loss by water erosion in the Winam Gulf catchment amounts to 10.71 Mt year-1, with a mean soil loss rate of 9.63 t ha-1 year-1. These findings highlight the need to consider dynamic factors within the RUSLE model and can prove vital for identifying areas of high erosion risk for future targeted investigation and conservation action.

Assessment of bioaccessibility and health risk of mercury within soil of artisanal gold mine sites, Niger, North-central part of Nigeria.

The occurrence of mercury (Hg) in the environment globally has been linked largely to its use for gold processing. In this research, ore samples, agricultural soil and mine wastes were taken within the vicinity of an artisanal gold mine and processing sites in Niger state, a north-central part of Nigeria to determine Hg contamination in the environment and estimate the potential hazard to health. The values of Hg measured in ore, agricultural soil and mine wastes ranged between 0.03 and 5.9, 0.002 and 5.57 and 0.19 and 20.99 mg/kg, respectively, with the majority of samples observed above the crustal average values of 0.003 mg/kg. All of the samples were 100 times greater than the USEPA residential soil screening level of 0.0023 mg/kg, but were lower than comparable mine sites within the same region. Contamination indices were used to demonstrate the potential exposure to Hg contamination in the study area which ranged from a medium to high level of contamination. Average daily dose and hazard quotient (HQ) were calculated for adults and children in the study area and decreased in the following order: ADDvapour > ADDingestion > ADDdermal > ADDinhalation. The non-carcinogenic health risk index (HI) of Hg calculated for children and adults in the study area was children: 7.42, 2.19, 1.49 and adults: 4.45, 1.26, 1.19, for mine wastes, agricultural soil and ore, respectively. All of these values were higher than a considered safe level (= 1) and therefore showed that Hg posed a serious non-carcinogenic HI for both adults and children exposed to the soil in the study area. The bioaccessible fraction as a measure of ingestion for Hg was generally < 13% across all sample matrices, suggesting a low bioaccessibility. An HQ incorporating bioaccessible data (BHQ) ranged between 0.000005 and 4.06 with a mean value of 0.62. Values for the BHQ were still > 1, threshold limit in some samples and showed that Hg could present a risk to health via ingestion, although further research is required to assess dermal and inhalation bioaccessibility to assess fully the risk to residents. However, the values were lower than the non-carcinogenic health risk index, which is assumed to be overestimated.