Geochemical composition and potential health risks of geophagic materials: an example from a rural area in the Limpopo Province of South Africa.

Geophagy is a common practice among rural population of the Fetakgomo Tubatse Local Municipality area in the Limpopo Province of South Africa. Although, the practice might be beneficial to the health of the consumers, its negative effects could overshadow the positive effects and might lead to detrimental health issues. The present work sought to investigate the geochemical composition as well as pH and organic matter (OM) content of geophagic materials commonly consumed in the study area. Furthermore, assessment of the potential health risk of the materials on geophagic individuals was also considered. Twelve samples were collected in the study area and analysed by X-ray Fluorescence (XRF) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) for major and trace elements composition. The results showed higher concentrations of non-essential elements (e.g., As, Cr, Pb) than the proposed recommended daily standards intake, suggesting a potential health risk. The alkaline nature (pH 6.80 to 9.22) of the studied samples might affect the bioacessibility of some essential elements. Furthermore, the OM content (> 0.7%) observed in some of the studied samples may retain pathogenic micro-organisms detrimental to health. Although As and Cr presented a low bioaccessible fraction (< 16.0%), health risk assessment revealed that their concentrations represented a hazard (HQ > 1) and might induce non-carcinogenic health threats to geophagic individuals. Based on the geochemical analysis, pH and OM content as well as health risk assessment findings, the studied geophagic materials are not considered suitable for human consumption. The practice should therefore be discouraged amongst the population in the study area to avoid possible detrimental health issues.

Chemical fractionation of particulate-bound metal(loid)s to evaluate their bioavailability, sources and associated cancer risk in India.

Eleven potentially toxic metal(loid)s (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), proven source markers of mineral based coal-fired industrial emissions and vehicular exhausts, were analysed using the four steps sequential extraction method to evaluate metal(loid)s concentration, in total and fractions of bioavailable and non-bioavailable for fine (PM2.5) and coarse (PM10-2.5) particulate modes. A total of 26-day-wise samples with three replications (total number of samples = 78) were collected in January-December 2019 for each PM10 and PM2.5 at an urban-residential site in India. In both the coarse and fine particulate modes, Pb and Cr have respectively shown the highest and lowest total concentrations of the measured metal(loid)s, indicating the presence of coal-fired power plants and heavy vehicular activities near to study area. In addition, Mn has shown highest bioavailable fraction for both coarse and fine particulate modes. More than 50 % of metal(loid)s concentration, in total to a bioavailable fraction (BAF) were observed in case of As, Cd, Cr, Co, Mn, Ni, and Pb of PM2.5. Mn and Zn have shown similar behaviour in the case of coarse particulate mode. Source apportionment of metal(loid)s bioavailable fractions using positive matrix factorization (PMF 5.0) has found three significant sources: crustal and natural dust (30.04 and 39 %), road traffic (49.57 and 20 %), and industrial emission (20.39 and 41 %) for coarse and fine particulate mode, respectively. Cancer risk through the inhalation pathway was high in total concentration but lower in BAF concentration in both age groups (children and adults).

Geochemical and mineralogical characterization of Ria de Aveiro (Portugal) saltpan sediments for pelotherapy application.

The present study aims to characterize sediments textural, geochemical and mineralogical composition used in a SPA for pelotherapy applications. Six samples were collected in two areas of an open-air saline SPA, a former saltpan in Ria de Aveiro (Portugal). Sampling areas are predominantly composed by recent alluvium that had been affected by chemical industrial effluents for over 50 years. Samples < 2000, 63, and 2 µm fractions were analyzed by X-ray Diffraction (XRD) and X-ray Fluorescence (XRF), for identification of mineral phases and chemical composition. SEM analysis was used for individual particles morphological characterization and chemical semi-quantification. Texture, mineral phases and chemical composition showed the influence of SPA pond beneficiation works. The two SPA areas revealed distinct mineral phases, one with higher quartz content, and the other with higher halite content, consistent with their environmental conditions. Illite constituted the most abundant mineral phase of the clay fraction. Preliminary results suggested concentrations of potential toxic elements (e.g., As, Cd) above reference values, representing a risk to the ecosystem and humans.

Archaeological and Chemical Investigation on Mortars and Bricks from a Necropolis in Braga, Northwest of Portugal.

This investigation intends to study and characterize the mortars and bricks from walls and floors used in the funerary nucleus of the archaeological site of Dr. Gonçalo Sampaio Street (Braga, Portugal), associated with the Via XVII necropolis of the Bracara Augusta Roman city. The diversity of the funeral structures and their exceptional state of conservation make this sector of the necropolis an unprecedented case and a reference site in the archaeology of Braga, a determinant for its conservation and musealization. Nineteen mortars samples were analysed by X-ray Fluorescence. The results showed clear chemical composition differences among coating and floor mortars (CFM), masonry mortars (MM) and bricks (B) groups of samples. The chemical affinity between CFM from the V to IV centuries, CFM from the IV to V centuries, MM from brick walls (IV-V centuries), MM from stone walls (V-VII centuries) and B from the IV to V centuries samples were confirmed by statistical analyses. Their composition was distinctly related to the use of different raw materials, according to their chronological context; in mortars, according to their function in the structures; and in some samples, from contamination.

Temporal fluctuations in water contamination from abandoned pyrite Wiesciszowice mine (Western Sudetes, Poland).

Production of acid mine drainage may occur during mining operations and may continue for many years after closure. In some cases, especially when host rock is capable of reacting with acidic drainage, metal concentrations may decrease over time and distance. Seasonal variations in water flow rate also play an important role in metals concentration both in surface and groundwater. The present study evaluates the contamination of an abandoned pyrite mining area (Wiesciszowice, SW Poland) and the temporal variation of the water contamination in selected locations of 2 sampling campaigns (2000 and 2015). The mining surrounding Rudawy Janowickie Mountains range is well known for the rich mining history and is considered as one of the oldest in Europe. The Wiesciszowice pyrite mine was exploited for several hundreds of years and processed Fe and Cu sulfides, and sulfur. This mine was closed in 1925 because of the high competition of pyrites from Spain. Results show clearly that water samples collected in the mining area are mainly Ca-SO4 and acid/high metal, while spring water and surface water samples, representing the local geochemical background, are Ca-HCO3 and neutral-low metal. The analysis of data shows an improvement in water quality from 2000 to 2015 as well as a decreasing of water risk assessment for human use. This improvement can be related to the fact that 2015 was a very dry year, with over 60% less flow than in 2000, leading to less water contamination.

Fine Particulate Matter and Gaseous Compounds in Kitchens and Outdoor Air of Different Dwellings.

Passive diffusion tubes for volatile organic compounds (VOCs) and carbonyls and low volume particulate matter (PM2.5) samplers were used simultaneously in kitchens and outdoor air of four dwellings. PM2.5 filters were analysed for their carbonaceous content (organic and elemental carbon, OC and EC) by a thermo-optical technique and for polycyclic aromatic hydrocarbon (PAHs) and plasticisers by GC-MS. The morphology and chemical composition of selected PM2.5 samples were characterised by SEM-EDS. The mean indoor PM2.5 concentrations ranged from 14 µg m-3 to 30 µg m-3, while the outdoor levels varied from 18 µg m-3 to 30 µg m-3. Total carbon represented up to 40% of the PM2.5 mass. In general, the indoor OC/EC ratios were higher than the outdoor values. Indoor-to-outdoor ratios higher than 1 were observed for VOCs, carbonyls and plasticisers. PAH levels were much higher in the outdoor air. The particulate material was mainly composed of soot aggregates, fly ashes and mineral particles. The hazard quotients associated with VOC inhalation suggested a low probability of non-cancer effects, while the cancer risk was found to be low, but not negligible. Residential exposure to PAHs was dominated by benzo[a]pyrene and has shown to pose an insignificant cancer risk.

Geochemical, Mineralogical and Morphological Characterisation of Road Dust and Associated Health Risks.

Road dust resuspension, especially the particulate matter fraction below 10 µm (PM10), is one of the main air quality management challenges in Europe. Road dust samples were collected from representative streets (suburban and urban) of the city of Viana do Castelo, Portugal. PM10 emission factors (mg veh-1 km-1) ranging from 49 (asphalt) to 330 (cobble stone) were estimated by means of the United Stated Environmental Protection Agency method. Two road dust fractions (< 0.074 mm and from 0.0074 to 1 mm) were characterised for their geochemical, mineralogical and morphological properties. In urban streets, road dusts reveal the contribution from traffic emissions, with higher concentrations of, for example, Cu, Zn and Pb. In the suburban area, agriculture practices likely contributed to As concentrations of 180 mg kg-1 in the finest road dust fraction. Samples are primarily composed of quartz, but also of muscovite, albite, kaolinite, microcline, Fe-enstatite, graphite and amorphous content. Particle morphology clearly shows the link with natural and traffic related materials, with well-formed minerals and irregular aggregates. The hazard quotient suggests a probability to induce non-carcinogenic adverse health effects in children by ingestion of Zr. Arsenic in the suburban street represents a human health risk of 1.58 × 10-4.

Review of the nature of some geophagic materials and their potential health effects on pregnant women: some examples from Africa.

The voluntary human consumption of soil known as geophagy is a global practice and deep-rooted in many African cultures. The nature of geophagic material varies widely from the types to the composition. Generally, clay and termite mound soils are the main materials consumed by geophagists. Several studies revealed that gestating women across the world consume more soil than other groups for numerous motives. These motivations are related to medicinal, cultural and nutrients supplementation. Although geophagy in pregnancy (GiP) is a universal dynamic habit, the highest prevalence has been reported in African countries such as Kenya, Ghana, Rwanda, Nigeria, Tanzania, and South Africa. Geophagy can be both beneficial and detrimental. Its health effects depend on the amount and composition of the ingested soils, which is subjective to the geology and soil formation processes. In most cases, the negative health effects concomitant with the practice of geophagy eclipse the positive effects. Therefore, knowledge about the nature of geophagic material and the health effects that might arise from their consumption is important.

The geochemistry of geophagic material consumed in Onangama Village, Northern Namibia: a potential health hazard for pregnant women in the area.

Ingestion of geophagic materials might affect human health and induce diseases by different ways. The purpose of this study is to determine the geochemical composition of geophagic material consumed especially by pregnant women in Onangama Village, Northern Namibia and to assess its possible health effects. X-ray fluorescence and inductively coupled plasma mass spectrometry were used in order to determine the major, and trace elements as well as anions concentrations of the consumed material. The geochemical analysis revealed high concentrations of aluminium (Al), calcium (Ca), iron (Fe), magnesium (Mg), manganese (Mn), potassium (K), sodium (Na), and silica (Si); and trace elements including arsenic (As), chromium (Cr), mercury (Hg), nickel (Ni) and vanadium (V) as well as sulphate (SO42-), nitrate (NO3-), and nitrite (NO2-) anions comparing to the recommended daily allowance for pregnant women. The pH for some of the studied samples is alkaline, which might increase the gastrointestinal tract pH (pH < 2) and cause a decrease in the bioavailability of elements. The calculated health risk index (HRI > 1) revealed that Al and Mn might be a potential risk for human consumption. Based on the results obtained from the geochemical analysis, the consumption of the studied material might present a potential health risk to pregnant women including concomitant detrimental maternal and foetal effects.

A review of exposure assessment methods for epidemiological studies of health effects related to industrially contaminated sites.

BACKGROUND: this paper is based upon work from COST Action ICSHNet. Health risks related to living close to industrially contaminated sites (ICSs) are a public concern. Toxicology-based risk assessment of single contaminants is the main approach to assess health risks, but epidemiological studies which investigate the relationships between exposure and health directly in the affected population have contributed important evidence. Limitations in exposure assessment have substantially contributed to uncertainty about associations found in epidemiological studies. OBJECTIVES: to examine exposure assessment methods that have been used in epidemiological studies on ICSs and to provide recommendations for improved exposure assessment in epidemiological studies by comparing exposure assessment methods in epidemiological studies and risk assessments. METHODS: after defining the multi-media framework of exposure related to ICSs, we discussed selected multi-media models applied in Europe. We provided an overview of exposure assessment in 54 epidemiological studies from a systematic review of hazardous waste sites; a systematic review of 41 epidemiological studies on incinerators and 52 additional studies on ICSs and health identified for this review. RESULTS: we identified 10 multi-media models used in Europe primarily for risk assessment. Recent models incorporated estimation of internal biomarker levels. Predictions of the models differ particularly for the routes 'indoor air inhalation' and 'vegetable consumption'. Virtually all of the 54 hazardous waste studies used proximity indicators of exposure, based on municipality or zip code of residence (28 studies) or distance to a contaminated site (25 studies). One study used human biomonitoring. In virtually all epidemiological studies, actual land use was ignored. In the 52 additional studies on contaminated sites, proximity indicators were applied in 39 studies, air pollution dispersion modelling in 6 studies, and human biomonitoring in 9 studies. Exposure assessment in epidemiological studies on incinerators included indicators (presence of source in municipality and distance to the incinerator) and air dispersion modelling. Environmental multi-media modelling methods were not applied in any of the three groups of studies. CONCLUSIONS: recommendations for refined exposure assessment in epidemiological studies included the use of more sophisticated exposure metrics instead of simple proximity indicators where feasible, as distance from a source results in misclassification of exposure as it ignores key determinants of environmental fate and transport, source characteristics, land use, and human consumption behaviour. More validation studies using personal exposure or human biomonitoring are needed to assess misclassification of exposure. Exposure assessment should take more advantage of the detailed multi-media exposure assessment procedures developed for risk assessment. The use of indicators can be substantially improved by linking definition of zones of exposure to existing knowledge of extent of dispersion. Studies should incorporate more often land use and individual behaviour.

Health risk assessment through consumption of vegetables rich in heavy metals: the case study of the surrounding villages from Panasqueira mine, Central Portugal.

Panasqueira mine is a tin-tungsten mineralization hosted by metasediments with quartz veins rich in ferberite. The mineralization also comprises wolframite, cassiterite, chalcopyrite, several sulfides, carbonates and silver sulfosalts. The mining and beneficiation processes produce arsenic-rich mine wastes laid up in huge tailings (Barroca Grande and Rio tailings). The contents of As, Cd, Cr, Cu, Pb and Zn were estimated in rhizosphere soils, irrigation waters, road dusts and in potatoes, cabbages, lettuces and beans, collected on local gardens of four neighborhood Panasqueira mine villages: S. Francisco de Assis (SFA) and Barroca suffering the influence of tailings; Unhais-o-Velho and Casegas considered as non-polluted areas. The mean concentrations of metals in rhizosphere soils and vegetables exceed the reference guidelines values and seem to be linked to the sulfides. The rhizosphere ecological risks were ranked in the order of Cd > As > Cu > Pb > Zn > Cr and SFA > Barroca > Casegas > Unhais-o-Velho. Metal concentrations, in vegetables, were found in the order of lettuce > cabbage > potatoes and SFA > Barroca > Casegas > Unhais-o-Velho. For cabbages and lettuces, the tendency of contamination is roots > leaves and for potatoes is roots > leaves > tubers. The risk for residents, due to ingesting of metals/metalloid, by consuming vegetables grown around the sampling area, was calculated and the result indicates that the inhabitants of these villages are probably exposed to some potential health risks through the intake of heavy metals and metalloids via consuming their vegetables.

Microbial diversity in deep-sea sediments from the Menez Gwen hydrothermal vent system of the Mid-Atlantic Ridge.

Deep-sea hydrothermal sediments are known to support remarkably diverse microbial consortia. Cultureindependent sequence-based technologies have extensively been used to disclose the associated microbial diversity as most of the microorganisms inhabiting these ecosystems remain uncultured. Here we provide the first description of the microbial community diversity found on sediments from Menez Gwen vent system. We compared hydrothermally influenced sediments, retrieved from an active vent chimney at 812 m depth, with non-hydrothermally influenced sediments, from a 1400 m depth bathyal plain. Considering the enriched methane and sulfur composition of Menez Gwen vent fluids, and the sediment physicochemical properties in each sampled area, we hypothesized that the site-associated microbes would be different. To address this question, taxonomic profiles of bacterial, archaeal and micro-eukaryotic representatives were studied by rRNA gene tag pyrosequencing. Communities were shown to be significantly different and segregated by sediment geographical area. Specific mesophilic, thermophilic and hyperthermophilic archaeal (e.g., Archaeoglobus, ANME-1) and bacterial (e.g., Caldithrix, Thermodesulfobacteria) taxa were highly abundant near the vent chimney. In contrast, bathyal-associated members affiliated to more ubiquitous phylogroups from deep-ocean sediments (e.g., Thaumarchaeota MGI, Gamma- and Alphaproteobacteria). This study provides a broader picture of the biological diversity and microbial biogeography, and represents a preliminary approach to the microbial ecology associated with the deep-sea sediments from the Menez Gwen hydrothermal vent field.

Integrated approach to assess the environmental impact of mining activities: estimation of the spatial distribution of soil contamination (Panasqueira mining area, Central Portugal).

Through the years, mining and beneficiation processes in Panasqueira Sn-W mine (Central Portugal) produced large amounts of As-rich mine wastes laid up in huge tailings and open-air impoundments (Barroca Grande and Rio tailings) that are the main source of pollution in the surrounding area once they are exposed to the weathering conditions leading to the formation of acid mine drainage (AMD) and consequently to the contamination of the surrounding environments, particularly soils. The active mine started the exploration during the nineteenth century. This study aims to look at the extension of the soil pollution due to mining activities and tailing erosion by combining data on the degree of soil contamination that allows a better understanding of the dynamics inherent to leaching, transport, and accumulation of some potential toxic elements in soil and their environmental relevance. Soil samples were collected in the surrounding soils of the mine, were digested in aqua regia, and were analyzed for 36 elements by inductively coupled plasma mass spectrometry (ICP-MS). Selected results are that (a) an association of elements like Ag, As, Bi, Cd, Cu, W, and Zn strongly correlated and controlled by the local sulfide mineralization geochemical signature was revealed; (b) the global area discloses significant concentrations of As, Bi, Cd, and W linked to the exchangeable and acid-soluble bearing phases; and (c) wind promotes the mechanical dispersion of the rejected materials, from the milled waste rocks and the mineral processing plant, with subsequent deposition on soils and waters. Arsenic- and sulfide-related heavy metals (such as Cu and Cd) are associated to the fine materials that are transported in suspension by surface waters or associated to the acidic waters, draining these sites and contaminating the local soils. Part of this fraction, especially for As, Cd, and Cu, is temporally retained in solid phases by precipitation of soluble secondary minerals (through the precipitation of hydrated metal sulfates) in warm, dry periods, but such minerals are easily dissolved during rainy periods. Climate is an important instability factor, and the hot and dry summers and cold, rainy, and windy winters in this region are physical phenomena that enhance the good receptivity of these soils to retain some of the metals present in the primary and also the secondary mineralogy. Considering the obtained results from both the sequential chemical extraction and the environmental risk assessment according to the risk assessment code, Ag, Cd, Cu, and Zn are classified with very high risk while As is classified with medium risk.

Quantitative-spatial assessment of soil contamination in S. Francisco de Assis due to mining activity of the Panasqueira mine (Portugal).

Through the years, mining and beneficiation processes produces large amounts of As-rich mine wastes laid up in huge tailings and open-air impoundments (Barroca Grande and Rio tailings) that are the main source of pollution in the surrounding area once they are exposed to the weathering conditions leading to the formation of AMD and consequently to the contamination of the surrounding environments, in particularly soils. In order to investigate the environmental contamination impact on S. Francisco de Assis (village located between the two major impoundments and tailings) agricultural soils, a geochemical survey was undertaken to assess toxic metals associations, related levels and their spatial distribution, and to identify the possible contamination sources. According to the calculated contamination factor, As and Zn have a very high contamination factor giving rise to 65.4% of samples with a moderate to high pollution degree; 34.6% have been classified as nil to very low pollution degree. The contamination factor spatial distribution put in evidence the fact that As, Cd, Cu, Pb, and Zn soils contents, downstream Barroca Grande tailing, are increased when compared with the local Bk soils. The mechanical dispersion, due to erosion, is the main contamination source. The chemical extraction demonstrates that the trace metals distribution and accumulation in S. Francisco de Assis soils is related to sulfides, but also to amorphous or poorly crystalline iron oxide phases. The partitioning study allowed understanding the local chemical elements mobility and precipitation processes, giving rise to the contamination dispersion model of the study area. The wind and hydrological factors are responsible for the chemical elements transport mechanisms, the water being the main transporter medium and soils as one of the possible retention media.