Metal(loid)s in urban soil from historical municipal solid waste landfill: Geochemistry, source apportionment, bioaccessibility testing and human health risks.

Landfills, especially those poorly managed, can negatively affect the environment and human beings through chemical contamination of soils and waters. This study investigates the soils of a historical municipal solid waste (MSW) landfill situated in the heart of a residential zone in the capital of Slovakia, Bratislava, with an emphasis on metal (loid) contamination and its consequences. Regardless of the depth, many of the soils exhibited high metal (loid) concentrations, mainly Cd, Cu, Pb, Sb, Sn and Zn (up to 24, 2620, 2420, 134, 811 and 6220 mg/kg, respectively), classifying them as extremely contaminated based on the geo-accumulation index (Igeo >5). The stable lead isotopic ratios of the landfill topsoil varied widely (1.1679-1.2074 for 206Pb/207Pb and 2.0573-2.1111 for 208Pb/206Pb) and indicated that Pb contained a natural component and an anthropogenic component, likely municipal solid waste incineration (MSWI) ash and construction waste. Oral bioaccessibility of metal (loid)s in the topsoil was variable with Cd (73.2-106%) and Fe (0.98-2.10%) being the most and least bioaccessible, respectively. The variation of metal (loid) bioaccessibility among the soils could be explained by differences in their geochemical fractionation as shown by positive correlations of bioaccessibility values with the first two fractions of BCR (Community Bureau of Reference) sequential extraction for As, Cd, Mn, Ni, Pb, Sn and Zn. The results of geochemical fractionation coupled with the mineralogical characterisation of topsoil showed that the reservoir of bioaccessible metal (loid)s was calcite and Fe (hydr)oxides. Based on aqua regia metal (loid) concentrations, a non-carcinogenic risk was demonstrated for children (HI = 1.59) but no risk taking into account their bioaccessible concentrations (HI = 0.65). This study emphasises the need for detailed research of the geochemistry of wastes deposited in urban soils to assess the potentially hazardous sources and determine the actual bioaccessibility and human health risks of the accumulated metal (loid)s.

Metal(loid) concentrations, bioaccessibility and stable lead isotopes in soils and vegetables from urban community gardens.

Community gardens are "green oases" of recent cities with many benefits for human society. From a human health perspective, these benefits can be damaged by chemical contamination of soil and cultivated vegetables. Using geochemical approaches, this study characterised (i) total metal(loid) concentrations in soils and two commonly grown vegetables in urban community gardens (Bratislava, Slovakia), (ii) gastrointestinal bioaccessibility using a modified physiologically based extraction test (PBET), and (iii) stable lead (Pb) isotopes in order to identify sources of metal(loid)s, solubilisation in the human body and migration of Pb from soil to vegetables. While some soils could be considered contaminated when compared to the Slovak legislation for agricultural soil, the bioaccessibility of metal(loid)s did not exceed 20% in the intestinal phase, with the exception of cadmium (Cd). Tomatoes and lettuce contained low total and bioaccessible concentrations of metal(loid)s, being safe for people who consume their own grown vegetables. There were differences in Pb isotope composition among bulk soils, vegetables and bioaccessible Pb, with less radiogenic Pb being preferentially mobilised. Statistical methods considering the compositional nature of the geochemical data and the enrichment factor (EF) distinguished well metal(loid)s of natural origin (As, Co, Cr, Fe, Mn, Ni, V) from those with anthropogenic contributions. This research has shown the usefulness of integrating different methodologies to better understand the geochemistry of metal(loid)s in urban soils with their highly diversified sources.

Sixteen priority polycyclic aromatic hydrocarbons in roadside soils at traffic light intersections (Bratislava, Slovakia): concentrations, sources and influencing factors.

Combustion of fossil fuels is the most important source of polycyclic aromatic hydrocarbons (PAHs) in the environment. Cities are typical of many human activities which are dependent on fossil fuels (road and railway transport, heat generation, waste incineration and industry) on a small area, leading to high concentrations of PAHs in urban air, dust and soil. The aim of this study was to determine the possible influence of urban traffic on the accumulation of sixteen priority PAHs in soils (n = 132 at two soil depths of 0-10 cm and 10-20 cm) taken at intersections (n = 37) with different traffic volumes and road ages. Variable concentrations of the sum of PAHs (∑16PAH) ranging from 188 to 21,950 µg/kg with a mean and median of 3021 µg/kg and 1930 µg/kg were recorded, respectively. Concentrations of PAHs positively correlated with soil organic carbon content (TOC) (rSpearman = 0.518; p < 0.001). Statistically significant positive correlations between ∑16PAH concentrations and traffic volume/road age were found in this study (rSpearman = 0.689/0.619; p < 0.001), while ∑16PAH concentration decreased with increasing distance from the road edge and was statistically lower at a soil depth of 10-20 cm than at 0-10 cm (p < 0.05). Multivariate statistical methods (principal component analysis and cluster analysis) applied to log-ratio transformed data (clr) to decrease the constant sum constraint coupled with positive matrix factorisation (PMF) modelling pointed to the dominance of pyrogenic emission sources, with 62.1% traffic-related (petrol and diesel emissions, liquid fuel and motor oil spills, and tyre wear) according to PMF results.

Concentrations of selected trace elements in surface soils near crossroads in the city of Bratislava (the Slovak Republic).

It is well known that road transport emits various trace elements into the environment, which are deposited in soils in the vicinity of roads, so-called roadside soils, and thus contributes to the deterioration of their chemical state. The aim of this work was to determine concentrations of some metals and metalloids (arsenic (As), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), antimony (Sb), vanadium (V), and zinc (Zn)) in soils from crossroads with traffic signals, which are characterized by deceleration of vehicles and increased emissions of elements related mainly to brake and tyre wear. The results confirmed a moderate enrichment of soils with Cu, Pb, and Zn (enrichment factor (EF) values > 2) and significant enrichment for Sb (EF > 5), while the other elements showed no or minimal enrichment. The age of crossroads proved to have a positive influence on the accumulation of some elements in soils with the largest differences for Cu, Fe, Pb, Sb, and Zn (p < 0.001). Traffic volumes expressed as the average daily traffic intensity (ADTI) also positively influenced soil concentrations of Cr, Cu, Pb, Sb, and Zn, while distance to the crossroad had a significant negative effect on the soil concentration of Cu, Sb, and Zn (p < 0.001). The stable isotopic ratios of Pb, 206Pb/207Pb and 208Pb/206Pb, ranging from 1.1414 to 1.2046 and from 2.0375 to 2.1246, respectively, pointed to the mixed natural-anthropic origin of Pb in the soils of crossroads with a visible contribution of traffic-related sources. Based on the above findings combined with covariance among the studied elements using statistical methods applied to compositionally transformed data, it was possible to show that Cu, Pb, Sb, and Zn clearly originated from road traffic.

Trace elements in two particle size fractions of urban soils collected from playgrounds in Bratislava (Slovakia).

Today, it is proven that the contaminated urban soils are hazardous for the human health. Soil substrates of playgrounds call for special research as they are places where children are directly exposed to soil contaminants. Therefore, the objective of this work was to measure the pseudo-total contents and bioaccessibility of several metals and metalloids (As, Bi, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Sn, V, Zn) in two grain sizes (< 150 µm and < 50 µm) of playground soils in Bratislava city (the capital of Slovakia). The content of metal(loid)s in the soils was controlled by a number of factors, with their increased contents (above 75% percentile or higher) at sites influenced by point sources of pollution (industry and agriculture) or at old sites located in the city centre. Cobalt, Cr, Fe, Mn, Ni and V had relatively uniform contents in soils compared to the other elements. As regression modelling with a categorical variable confirmed, the age of urban areas influenced the accumulation of As, Bi, Cd, Cu, Hg, Pb, Sb and Sn in playground soils. Exploratory statistical techniques with compositionally transformed data (principal component analysis, cluster analysis and construction of symmetric coordinates for correlation analysis) divided trace elements into the two main groupings, Co, Cr, Fe, Mn, Ni, V and Bi, Cd, Cu, Hg, Pb, Sb, Sn, Zn. Median concentrations of the elements in smaller soil grains (< 50 µm) were significantly higher than in coarser grains (< 150 µm). Cobalt, Cu, Mn, Pb, Sn and Zn had significantly higher bioaccessible proportions (% of the pseudo-total content) in < 50 µm soil size than in < 150 µm; however, the same order of bioaccessibility was achieved in both grain sizes. The highest bioaccessibility had Cd, Cu, Pb and Zn (~ 40% and more), followed by Co, As, Mn, Sb (18-27%), Hg, Ni, Sn (10-12%) and finally Cr, Fe and V (less than 4%). The hazard index and carcinogenic risk values were higher in < 50 µm than in < 150 µm and significantly decreased in the two soil sizes when the bioaccessibility results were included in the health hazard calculation.

Total mercury, chromium, nickel and other trace chemical element contents in soils at an old cinnabar mine site (Merník, Slovakia): anthropogenic versus natural sources of soil contamination.

The aims of this study were to investigate the occurrence and distribution of total mercury (Hg) and other trace elements of environmental concern, such as arsenic (As), copper (Cu), chromium (Cr), manganese (Mn), nickel (Ni), lead (Pb), zinc (Zn) and vanadium (V), in soils from the abandoned Merník cinnabar mine in eastern Slovakia. For this purpose, thirty soil samples from two depth intervals within the mine area (n = 60 soil samples) and additional sixteen soil samples from adjacent areas (n = 25 soil samples) were collected. Total Hg was measured by atomic absorption spectrometry, while As and other metals were analyzed using inductively coupled plasma atomic emission spectrometry. High mercury concentrations (> 100 mg/kg with a maximum of 951 mg/kg) were observed only in surface soils close to mine waste heaps and adits. Otherwise, Hg concentrations in the majority of surface soils were lower (0.14-19.7 mg/kg), however, higher than Hg in soils collected from sites outside the mine area (0.19-6.92 mg/kg) and even considerably higher than Hg in soils at sites not influenced by the Merník mine. Elevated Cr and Ni concentrations in soils regardless of their sampling sites (mean of 276 mg/kg and median of 132 mg/kg for Cr and 168 mg/kg and 81 mg/kg for Ni, respectively) were attributed to the lithology of the area; the soils are underlain by the sediments of the Central Carpathian Palaeogene, containing a detritus of ultrabasic rocks. As our geochemical data are compositional in nature, they were further treated by compositional data analysis (CoDA). Robust principal component analysis (RPCA) applied on centred (clr) log-ratio-transformed data and correlation analysis of compositional parts based on symmetric balances distinguished very well different sources of origin for the chemical elements. The following three element associations were identified: Hg association with the main source in mining/roasting, Cr-Ni association derived from bedrock and As-Cu-Mn-Pb-Zn-V association (natural background and minor sulphides/sulfosalts in mineralized rocks). The values of geoaccumulation index and enrichment factor suggested that concentrations of Hg in the soils were influenced by human industrial activities.

Flawed self-assessment in hand hygiene: A major contributor to infections in clinical practice?

AIM: To assess the quality of self-assessment and the attitude of healthcare workers (HCWs) to hand hygiene (HH) as possible factors of unsatisfactory HH compliance in clinical practice. BACKGROUND: Noncompliance of HH causes healthcare-acquired infections (HAI) in patients. It is assumed that HH-related infections make up approximately 80% of all infections in clinical practice. Our observations suggest that self-assessment and attitude might be surprisingly important factors. DESIGN AND METHOD: The cross-sectional approach using questionnaire and direct observation was applied. We followed STROBE guidelines. In total, questionnaires of 639 HCWs of surgical departments were included in the study, and 127 HCWs had been also directly observed. RESULTS: High self-assessment regarding HH compliance and its knowledge was reported by 74% and 83% of HCWs, respectively. At the same time, only 51% of HCWs positively evaluated their colleagues with respect to HH. Similar to previous studies, we have found significant differences between physicians and nurses regarding the level of self-assessment, attitude and perception of HH. Physicians were more critical in self-assessment and considered HH less important compared to nurses. The observations revealed drawbacks in HH practices. The high level of self-overassessment might be a contributing factor to noncompliance with HH. CONCLUSIONS: It is necessary to establish systematic professional training and education of HCWs in relation to their HH, and to continuously monitor and evaluate the level of self-assessment in clinical practice, mainly in surgery. RELEVANCE TO CLINICAL PRACTICE: A reasonable objective level of self-assessment and attitude to HH are the most important conditions for preventing of HAI in patients.

Arsenic in Playground Soils from Kindergartens and Green Recreational Areas of Bratislava City (Slovakia): Occurrence and Gastric Bioaccessibility.

In this study, playground soils of kindergartens and green recreational zones in Bratislava were investigated for the occurrence and gastric bioaccessibility of arsenic (As) in the < 150 µm soil size fraction. Eighty topsoil (0-10 cm) samples were collected from playgrounds in kindergartens and green recreational zones throughout the urban area. Bioaccessibility measurements of As were performed using the Simple Bioaccessibility Extraction Test that mimics the human gastric environment, and resulting extracts were analyzed by hydride generation-atomic absorption spectrometry to assess bioaccessible As concentrations in the collected playground soils. Single selective chemical extractions using hydroxylamine hydrochloride-hydrochloric acid and dithionite-citrate-bicarbonate solutions also were used to determine the amount of As associated with amorphous and amorphous/crystalline Fe oxy-hydroxides in soils, respectively. The results showed that the spatial distribution of total As concentrations was related to the historical development of the city, with higher soil concentrations of As found in the old city centre and related urban zones and the lower ones on the outskirts of Bratislava. There was a variation in the values of bioaccessible concentrations and fractions of As, with ranges from 0.40 to 5.60 mg/kg and 7.29 to 56.1%, respectively. Correlation and multivariable linear regression analyses revealed that bioaccessible concentrations of As were linearly related to its total concentrations in the soils, whereas dithionite-citrate-bicarbonate extractable Fe (FeDCB) was the main soil property, controlling the bioaccessibility of As. When the amount of FeDCB in the soils increased, As bioaccessibility decreased, confirming an importance of Fe bound to amorphous and crystalline iron oxy-hydroxides to the limitation of As bioaccessibility in urban playground soils of Bratislava. Additionally, single selective extractions showed that As concentrations extracted by hydroxylamine hydrochloride (AsHH) and dithionite-citrate-bicarbonate (AsDCB) were positively correlated with its bioaccessible concentrations (Spearman r = 0.75 and 0.62, respectively; p < 0.001).

Occurrence of selected trace metals and their oral bioaccessibility in urban soils of kindergartens and parks in Bratislava (Slovak Republic) as evaluated by simple in vitro digestion procedure.

A total of eighty surface soil samples were collected from public kindergartens and urban parks in the city of Bratislava, and the <150µm soil fraction was evaluated for total concentrations of five metals, Cd, Cu, Hg, Pb and Zn, their oral bioaccessibilities, non-carcinogenic and carcinogenic health risks to children, and lead isotopic composition. The mean metal concentrations in urban soils (0.29, 36.1, 0.13, 30.9 and 113mg/kg for Cd, Cu, Hg, Pb and Zn, respectively) were about two times higher compared with background soil concentrations. The order of bioaccessible metal fractions determined by Simple Bioaccessibility Extraction Test was: Pb (59.9%) > Cu (43.8%) > Cd (40.8%) > Zn (33.6%) > Hg (12.8%). Variations in the bioaccessible metal fractions were mainly related to the total metal concentrations in urban soils. A relatively wide range of lead isotopic ratios in urban soils (1.1598-1.2088 for 206Pb/207Pb isotopic ratio) indicated a combination of anthropogenic and geogenic sources of metals in the soils. Lower values of 206Pb/207Pb isotopic ratio in the city centre and similar spatial distribution of total metal concentrations, together with their increasing total concentrations in soils towards the city centre, showed that traffic and coal combustion in former times were likely the major sources of soil contamination. The non-carcinogenic and carcinogenic health risks to children due to exposure to metals in kindergarten and urban park soils were low, with hazard index and cancer risk values below the threshold values at all studied sites.