Investigating the impacts of heavy metal(loid)s on ecology and human health in the lower basin of Hungary's Danube River: A Python and Monte Carlo simulation-based study.

This study aimed to determine the environmental and health risks of the heavy metal levels in the Danube River in Hungary. The metals, including Fe, Mn, Zn, Cu, Ni, Cr, Pb, and As, were measured in the period from 2013 to 2019. The Spearman correlation and heatmap cluster analysis were utilized to determine the origin of pollution and the factors that control surface water quality. Several indices, such as the heavy metal pollution index (HPI), metal index (MI), hazard quotient oral and dermal (HQ), hazard index oral and dermal (HI), and carcinogenic risk (CR), were conducted to evaluate the potential risks for the environment and human health. The values of the HPI were between the range of 15 < HPI < 30, which indicated moderate pollution; however, the MI results showed high pollution in Dunaföldvár and Hercegszántó cities. The ecological risk (RI < 30) and HI values (< 1) showed low environmental risks and non-carcinogenic impacts of the existing metals, either on adults or children. The mean CR value of oral arsenic was 2.2E-04 and 2.5E-04 during April-September and October-March, respectively, indicating that children were the most vulnerable to arsenic-carcinogenic oral effects. While lead's CR oral values for children during April-September exceeded the threshold of 1.0E-04, chromium's oral and dermal CR values for both adults and children were 2.08E-04, 6.11E-04, 1.97E-04, and 5.82E-04 during April-September and October-March, respectively. These results demonstrate the potential carcinogenic risks related to chromium exposure within the two pathways in Hungary and highlight the need for effective measures to mitigate these risks.

Biomonitoring and assessment of toxic element contamination in floodplain sediments and soils using fluorescein diacetate (FDA) enzymatic activity measurements: evaluation of possibilities and limitations through the case study of the Drava River floodplain.

The EU Water Framework Directive requires the monitoring and evaluation of surface water sediment quality based on the assessment of risk posed by contamination on the biotic receptors. Floodplain sediments are important receptors of potentially toxic element (PTE) contamination from the upstream catchment areas, and floodplains host climate-sensitive riverine ecosystems and fertile agricultural areas at the same time. This study investigates the effect of PTE contamination on microbial communities in floodplain sediments and soils using the fast, inexpensive and reliable fluorescein diacetate (FDA) method in order to estimate its applicability for sediment quality monitoring and preliminary toxicity-based risk assessment. Sediment and soil samples were collected from the actively flooded alluvial plain and the river terrace areas along a 130-km stretch of the large Drava River floodplain known to be widely contaminated by historical mining, smelting and the associated industry in the upstream Alpine region. Results of detailed data analysis show that the total microbial activity represented by the measured FDA values is related to PTE (As, Cu, Zn, Cd, Pb) concentrations, but this relationship shows significant heterogeneity and depends on the spatial location and on the soil properties such as organic matter content, dissolved salt and nutrient content, and it is specific to the toxic elements. Results show that some microbe species appear to be able to adapt to the elevated PTE concentrations in toxic soil micro-environments, over time. Despite the observed heterogeneity of microbial activity, the results revealed a breakpoint in the FDA dataset around the FDA = 3 FC (fluorescein concentration) value suggesting that microbial activity is controlled by thresholds.

Advances in the use of recycled non-ferrous slag as a resource for non-ferrous metal mine site remediation.

The growing global demand for non-ferrous metals has led to serious environmental issues involving uncovered mine site slag dumps that threaten the surrounding soils, surface waters, groundwater, and the atmosphere. Remediation of these slags using substitute cement materials for ordinary Portland cement (OPC) and precursors for alkali-activated materials (AAMs) can convert hazardous solid wastes into valuable construction materials, as well as to attain the desired solidification and stabilization (S/S) of heavy metal(loid)s (HM). This review discusses the current research on the effect of non-ferrous slags on the reaction mechanisms of the OPC and AAM. The S/S of HM from the non-ferrous slags in AAM and OPC is also reviewed. HM can be stabilized in these materials based on the complex salt effect and isomorphic effects. The major challenges faced in AAMs and OPC for HM stabilization include the long-term durability of the matrix (e.g., sulfate attack, stability of volume). The existing knowledge gaps and future trends for the sustainable application of non-ferrous slags are also discussed.

Arundo donax L. stem-derived biochar increases As and Sb toxicities from nonferrous metal mine tailings.

Toxic metal(loid)s released from tailing residues of mining operations have become a global issue with regard to environmental impacts. Biochar derived from the agriculture waste is considered as a cost-effective and stable material, which could be applied for remediation of sites contaminated with toxic metal(loid)s. In the present study, tailings were amended for 90 days with increasing concentrations of Arundo donax L. stem-derived biochar (ASBC; at 0, 1, 3, and 5%). The 7-day wheat seed germination toxicity test was then used to assess the bioavailability of toxicants in aqueous leachates of the biochar-amended tailing samples. Concentrations of As, Cd, Cu, Pb, and Sb in leachates and the Community Bureau of Reference chemical fractions were determined using ICP-OES. The results indicated that tailing leachates were phytotoxic, an effect that was partially decreased due to increasing concentrations of ASBC, with maximum effects (∼47% of tailing phytotoxicity) occurring at 3% ASBC. Results of further fractionation analyses indicated that increasing concentrations of ASBC amendment decreased the mobile fractions of Cd, Cu, and Pb in tailing samples, but increased the mobilities of As and Sb. A novel approach using the relative toxicity index (= sum of toxicities of individual potentially toxic elements) indicated that the toxicity of the tailings decreased when As was not present, since As decreased the biochar-reduced toxicity. Our results suggest that the ability of using biochar to decrease toxicity in tailings (by sequestration of cationic metals such as Cd, Cu, and Pb) is limited by its inability to immobilize oxyanionic metalloids such as As and Sb.

Effects of typical flotation reagent on microbial toxicity and nickel bioavailability in soil.

The combined toxicological effects of nickel (Ni) and butyl xanthate (BX), that is commonly used in flotation reagents for non-ferrous metals ore processing such as Ni, copper and lead ores, on soil microbial communities were studied by determining soil microbial activity, soil enzyme activities and Ni bioavailability. The results revealed that the exchangeable (EXC) and reducible (RED) fractions of Ni were higher in Ni/BX mixture than Ni alone, probably because BX reacts with Ni to form complexes that lead an increase in bioavailability of Ni. The presence of BX and Ni inhibited microbial activity and enzyme activities during the first 30-days. Then, from 30 days to 180 days, different trends were observed according to the condition: microbial activity was stimulated with BX alone while it was inhibited with Ni/BX mixture. This observation was supported by the fact that the inhibitory ratio (I) was higher for Ni/BX mixture than BX alone. Results showed that the sensitivity to one or both contaminants followed the order: urease (UA) > invertase (INV). EXC fraction of Ni/BX mixture were significantly correlated with UA, INV, I, peak power (Ppeak) and peak time (Tpeak), respectively (p < 0.01), suggesting that Ni bioavailability might explain the Ni toxicity against microbial communities under combined pollution conditions. Such observations allow us to better understand toxic effects of Ni pollution when accompanied with BX, facilitating precisely evaluation of potential risks in mining areas.

Microcalorimetry and enzyme activity to determine the effect of nickel and sodium butyl xanthate on soil microbial community.

In non-ferrous metal tailings, combined pollution in the surrounding soil is caused by heavy metals and flotation chemicals. The combined effects of nickel (Ni) and its primary ore processing collector, sodium butyl xanthate (SBX), on soil microbial activity were investigated following the fluorescein diacetate hydrolase (FDA) and sucrase (SA) activities, and isothermal microcalorimetry during 60 days. FDA and SA activities as well as overall soil microbial activity were significantly affected by Ni, SBX and Ni/SBX mixture. The inhibition rate (I) of the growth rate constant (k) being higher with the Ni/SBX mixture than with SBX alone during the experiment. The growth rate constant (k) was positively correlated (p < 0.05 or p < 0.01) with enzyme activities (FDA and SA) indicating that k represented a valuable proxy to evaluate the toxic effect of metals and flotation reagents on soil microorganisms. Thus, microcalorimetry was a useful method to characterize soil microbial communities.

China's most typical nonferrous organic-metal facilities own specific microbial communities.

The diversity and function of microorganisms have yet to be explored at non-ferrous metal mining facilities (NMMFs), which are the world's largest and potentially most toxic sources of co-existing metal(loid)s and flotation reagents (FRs). The diversity and inferred functions of different bacterial communities inhabiting two types of sites (active and abandoned) in Guangxi province (China) were investigated for the first time. Here we show that the structure and diversity of bacteria correlated with the types of mine sites, metal(loid)s, and FRs concentrations; and best correlated with the combination of pH, Cu, Pb, and Mn. Combined microbial coenobium may play a pivotal role in NMMFs microbial life. Arenimonas, specific in active mine sites and an acidophilic bacterium, carries functions able to cope with the extreme conditions, whereas Latescibacteria specific in abandoned sites can degrade organics. Such a bacterial consortium provides new insights to develop cost-effective remediation strategies of co-contaminated sites that currently remain intractable for bioremediation.

Spatial relationship between the field-measured ambient gamma dose equivalent rate and geological conditions in a granitic area, Velence Hills, Hungary: An application of digital spatial analysis methods.

In order to estimate the annual dose that the public receive from natural radioactivity, the identification of the potential risk areas is required which, in turn, necessitates understanding the relationship between the spatial distribution of natural radioactivity and the geogenic risk factors (e.g., rock types, presence of dikes, faults, physical conditions of soil, etc.). A detailed spatial analysis of outdoor ambient gamma dose equivalent rate was performed in the western side of Velence Hills, the largest outcropped granitic area in Hungary. In order to assess the role of local geology in the spatial distribution of gamma dose rates, field measurements were carried out at ground level at 300 sites along a 250 m x 250 m regular grid in a total surface of 19.8 km2. Digital image processing methods were applied to identify anomalies, heterogeneities and spatial patterns in the measured gamma dose rates, including local maxima and minima determination, digital cross sections, gradient magnitude and gradient direction, second derivative profile curvature, local variability, lineament density, 2D autocorrelation and directional variogram analyses. Statistical inference shows that different gamma dose rate levels are associated with the geological formations, with the highest level on the Carboniferous granite including outlying values. Moreover, digital image processing reveales that linear gamma dose rate spatial features are parallel to the SW-NE dike system and to the NW-SE main fractures. The results of this study underline the importance of understanding the role of geogenic risk factors influencing the ambient gamma dose equivalent rate received by public. The study also demonstrates the power of the image processing techniques for the identification of spatial pattern in field-measured geogenic radiation.

Combined effects of antimony and sodium diethyldithiocarbamate on soil microbial activity and speciation change of heavy metals. Implications for contaminated lands hazardous material pollution in nonferrous metal mining areas.

The combined effects of antimony (Sb) and sodium diethyldithiocarbamate (DDTC), a common organic flotation reagent, on soil microbial activity and speciation changes of heavy metals were investigated for the first time. The results showed that the exchangeable fraction of Sb was transformed to a stable residual fraction during the incubation period, and the addition of DDTC promoted the transformation compared with single Sb pollution, probably because DDTC can react with heavy metals to form a complex. In addition, the presence of DDTC and Sb inhibited the soil microbial activity to varying degrees. The growth rate constant k of different interaction systems was in the following order on the 28th day: control group ≥ single DDTC pollution > combined pollution > single Sb pollution. A correlation analysis showed that the concentration of exchangeable Sb was the primary factor that affected the toxic reaction under combined pollution conditions, and it significantly affected the characteristics of the soil microorganisms. All the observations provide useful information for a better understanding of the toxic effects and potential risks of combined Sb and DDTC pollution in antimony mining areas.

Spatial analysis of ambient gamma dose equivalent rate data by means of digital image processing techniques.

A detailed ambient gamma dose equivalent rate mapping based on field measurements at ground level and at 1 m height was carried out at 142 sites in 80 × 90 km area in Pest County, Hungary. Detailed digital image processing analysis was carried out to identify and characterise spatial features such as outlying points, anomalous zones and linear edges in a smoothed TIN interpolated surface. The applied method proceeds from the simple shaded relief model and digital cross-sections to the more complex gradient magnitude and gradient direction maps, 2nd derivative profile curvature map, relief map and lineament density map. Each map is analysed for statistical characteristics and histogram-based image segmentation is used to delineate areas homogeneous with respect to the parameter values in these maps. Assessment of spatial anisotropy is implemented by 2D autocorrelogram and directional variogram analyses. The identified spatial features are related to underlying geological and tectonic conditions using GIS technology. Results show that detailed digital image processing is efficient in revealing the pattern present in field-measured ambient gamma dose equivalent rates and they are related to regional scale tectonic zones and surface sedimentary lithological conditions in the study area.

Mapping the geogenic radon potential: methodology and spatial analysis for central Hungary.

A detailed geogenic radon potential (GRP) mapping based on field soil gas radon and soil gas permeability measurements was carried out in this study. A conventional continuous variable approach was used in this study for GRP determination and to test its applicability to the selected area of Hungary. Spatial pattern of soil gas radon concentration, soil permeability and GRP and the relationship between geological formations and these parameters were studied by performing detailed spatial analysis. Exploratory data analysis revealed that higher soil gas radon activity concentration and GRP characterizes the mountains and hills than the plains. The highest values were found in the proluvial-deluvial sediments, rock debris on the downhill slopes eroded from hills. Among the Quaternary sediments, which characterize the study area, the fluvial sediment has the highest values, which are also located in the hilly areas. The lowest values were found in the plain areas covered by drift sand, fluvioeolic sand, fluvial sand and loess. As a conclusion, radon is related to the sediment cycle in the study area. A geogenic radon risk map was created, which assists human health risk assessment and risk reduction since it indicates the potential of the source of indoor radon. The map shows that low and medium geogenic radon potential characterizes the study area in central Hungary. High risk occurs only locally. The results reveal that Quaternary sediments are inhomogeneous from a radon point of view, fluvial sediment has medium GRP, whereas the other rock formations such as drift sand, fluioeolic sand, fluvial sand and loess, found in the study area, have low GRP.

Radon and thoron levels, their spatial and seasonal variations in adobe dwellings - a case study at the great Hungarian plain.

Radon and thoron isotopes are responsible for approximately half of the average annual effective dose to humans. Although the half-life of thoron is short, it can potentially enter indoor air from adobe walls. Adobe was a traditional construction material in the Great Hungarian Plain. Its major raw materials are the alluvial sediments of the area. Here, seasonal radon and thoron activity concentrations were measured in 53 adobe dwellings in 7 settlements by pairs of etched track detectors. The results show that the annual average radon and thoron activity concentrations are elevated in these dwellings and that the proportions with values higher than 300 Bq m(-3) are 14-17 and 29-32% for radon and thoron, respectively. The calculated radon inhalation dose is significantly higher than the world average value, exceeding 10 mSv y(-1) in 7% of the dwellings of this study. Thoron also can be a significant contributor to the inhalation dose with about 30% in the total inhalation dose. The changes of weather conditions seem to be more relevant in the variation of measurement results than the differences in the local sedimentary geology. Still, the highest values were detected on clay. Through the year, radon follows the average temperature changes and is affected by the ventilation, whereas thoron rather seems to follow the amount of precipitation.

Dynamics of soil gas radon concentration in a highly permeable soil based on a long-term high temporal resolution observation series.

This paper studies the temporal variation of soil gas radon activity concentration in a highly permeable (k = 2.0E-11 m(2)) sandy-gravelly soil in order to understand if temporal variation of soil gas radon activity concentration can affect geogenic radon potential determination. Geogenic radon potential provides information about the potential risk from radon. Its calculation takes into account the equilibrium, saturated at infinite depth, soil gas radon activity concentration (c∞). This concentration may vary at annual time scale due to the environmental conditions. A long-term (yearly) and high temporal resolution (15 min) observation, applied in this study, reveal various temporal features such as long-term trend, seasonality, daily periodicity and sudden events in soil gas radon time series. Results show seasonal and daily periodical variation of the measured soil gas radon activity concentration (csoilRn) in a highly permeable sandy-gravelly soil with definite seasons without obvious long transitional periods. The winter (from October 2010 to April 2011) is characterized by 2.5 times higher average soil gas radon activity concentration (median is 7.0 kBq m(-3)) than the summer (August, September 2010 and May, June, July 2011) (median is 2.8 kBq m(-3)). Daily periodicity, which is much less than the seasonal one, controls the soil gas radon activity concentration mainly in the summer season. Average (AM) value of csoilRn is higher at night than in the daytime with about 18% and 3.8% in summer and in winter, respectively. As a conclusion, in case of single csoilRn measurement on a highly permeable (k ≥ 2.0E-11 m(2)) soil, similar to our test site, csoilRn should be corrected according to the seasons for calculating the equilibrium activity concentration c∞ value.

Decision support methods for the environmental assessment of contamination at mining sites.

Polluting mine accidents and widespread environmental contamination associated with historic mining in Europe and elsewhere has triggered the improvement of related environmental legislation and of the environmental assessment and management methods for the mining industry. Mining has some unique features such as natural background pollution associated with natural mineral deposits, industrial activities and contamination located in the three-dimensional sub-surface space, the problem of long-term remediation after mine closure, problem of secondary contaminated areas around mine sites and abandoned mines in historic regions like Europe. These mining-specific problems require special tools to address the complexity of the environmental problems of mining-related contamination. The objective of this paper is to review and evaluate some of the decision support methods that have been developed and applied to mining contamination. In this paper, only those methods that are both efficient decision support tools and provide a 'holistic' approach to the complex problem as well are considered. These tools are (1) landscape ecology, (2) industrial ecology, (3) landscape geochemistry, (4) geo-environmental models, (5) environmental impact assessment, (6) environmental risk assessment, (7) material flow analysis and (8) life cycle assessment. This unique inter-disciplinary study should enable both the researcher and the practitioner to obtain broad view on the state-of-the-art of decision support methods for the environmental assessment of contamination at mine sites. Documented examples and abundant references are also provided.

Time variations of 222Rn concentration and air exchange rates in a Hungarian cave.

A long-term radon concentration monitoring was carried out in the Pál-völgy cave, Budapest, Hungary, for 1.5 years. Our major goal was to determine the time dependence of the radon concentration in the cave to characterise the air exchange and define the most important environmental parameters that influence the radon concentration inside the cave. The radon concentration in the cave air was measured continuously by an AlphaGuard radon monitor, and meteorological parameters outside the cave were collected simultaneously. The air's radon concentration in the cave varied between 104 and 7776 Bq m(-3), the annual average value was 1884±85 Bq m(-3). The summer to winter radon concentration ratio was as high as 21.8. The outside air temperature showed the strongest correlation with the radon concentration in the cave, the correlation coefficient (R) was 0.76.