Honeybees and their products as potential bioindicators of heavy metals contamination

The concentrations of three representative heavy metals(cadmium, chromium and lead) were measured by atomic absorptionspectroscopy in honeybees and in apiary's products (honey,pollen, propolis, and wax). Samples were collected from fivedifferent sampling points: four from areas surrounding the cityof Rome, and the fifth in the city center which receives intensevehicular traffic. All apiaries employed for this study werespecifically constructed without any metal part in order toavoid the risk of contamination of the assayed materials.Sample collection was conducted over a 3-month period (6samplings for honey and pollen, 3 sampling for propolis and wax,2 samplings for honeybees, all of which were collected in duplicate). Experimental data revealed, in general,statistically significant differences between the backgroundlevels of heavy metals recorded from the reference sites and thelevels measured in the site located in the center of the city ofRome.These results indicate that honeybees and, to a lesser extent,some of their products (pollen, propolis, wax, but not honey),can be considered representative bioindicators of environmentalpollution.     

Honeybees (<Emphasis Type="Italic">Apis mellifera</Emphasis>) as a biological barrier for contamination of honey by environmental toxic metals

The aim of the study was to investigate the transfer of toxic metals from honeybee workers (Apis mellifera L.) to bee honey in relation to the ecological state of the environment. The materials of the study consisted of samples of honeybee bodies and varietal honeys taken from the same apiary located in three areas: R1—urbanized (16), R2—ecologically clean (16) and R3—industrialized (15) of south-eastern Poland. The contents of 14 elements in all tested samples, including toxic metals (Cd, Pb, Hg, Al, Ni, Tl) as well as bioelements (K, Mg, Ca, Mn, Fe, Zn, Cu, Se), were analysed by the ICP-OES method with prior microwave mineralization. The concentrations of the majority of the studied elements, excluding aluminum and lead, were significantly higher in bee bodies than in honey samples (P?<?0.05). The pollution of bee bodies by toxic metals was dependent on the environmental cleanliness, and the most pollution was observed in the industrialized area. The bee body was the most effective barrier for Cd and Tl transfer to the honey, while the level of Ni was similar in both tested materials. The Al concentration was significantly higher in honey than bee bodies (14.81?±?24.69 and 6.51?±?5.83 mg kg^?1, respectively), which suggests the possibility of secondary contamination of honey. The greatest sensitivity to heavy metal pollution was observed in honeydew honey compared to nectar honeys (P?<?0.05). It was proved for the first time that bees work as biofilters for toxic metals and prevent honey contamination.     

Spatial and temporal variation of metal concentrations in adult honeybees (Apis mellifera L.)

Honeybees (Apis mellifera L.) have great potential for detecting and monitoring environmental pollution, given their wide-ranging foraging behaviour. Previous studies have demonstrated that concentrations of metals in adult honeybees were significantly higher at polluted than at control locations. These studies focused at a limited range of heavy metals and highly contrasting locations, and sampling was rarely repeated over a prolonged period. In our study, the potential of honeybees to detect and monitor metal pollution was further explored by measuring the concentration in adult honeybees of a wide range of trace metals, nine of which were not studied before, at three locations in the Netherlands over a 3-month period. The specific objective of the study was to assess the spatial and temporal variation in concentration in adult honeybees of Al, As, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ti, V and Zn. In the period of July-September 2006, replicated samples were taken at 2-week intervals from commercial-type bee hives. The metal concentration in micrograms per gram honeybee was determined by inductive coupled plasma-atomic emission spectrometry. Significant differences in concentration between sampling dates per location were found for Al, Cd, Co, Cr, Cu, Mn Sr, Ti and V, and significant differences in average concentration between locations were found for Co, Sr and V. The results indicate that honeybees can serve to detect temporal and spatial patterns in environmental metal concentrations, even at relatively low levels of pollution.     

Recovery assessment of a refined-oil impacted and fire ravaged mangrove ecosystem

An assessment of the diversity and abundance of macrobenthic community in a refined-oil (petrol) impacted and fire-ravaged mangrove ecosystem within the vicinity of a marine receipt terminal facility (Atlas Cove) serving as a distribution and pump station for refined products was carried out. The mangrove ecosystem was subjected to massive petrol spillage from a leaking pipeline and eventual fire outbreak. Following rehabilitation activities, a recovery assessment of the impacted ecosystem was carried out. The field surveys revealed that the petrol leakage and fire outbreak resulted in a near complete destruction of the mangrove ecosystem around the Atlas Cove depot, with macrobenthic species diversity index ranging between 0−0.4, compared to 0.78−0.87 in the control stations. The dominant early arrivals or colonizers of the impacted stations areas were Clibanarius africanus and Callinectes amnicola. Early signs of recovery of the impacted area were observed within about two and a half (2 1/2) to three (3) months, based on diversity and abundance indices respectively. The period of early signs of recovery also coincide with an observed reduction in the total hydrocarbon content (THC) levels in the sediment collected from the impacted stations by about nine folds from 3.67 mg/kg to 0.42 mg/kg within 3 months. Despite the apparent signs of recovery, the need for long-term monitoring of the impacted stations was discussed.     

Multiple approaches to assess the safety of artisanal marine food in a tropical estuary

In this study, metal and metalloid concentrations and pathogens were measured in shellfish at different locations in a tropical estuary, including sites impacted by sewage and industry. Oyster, mangrove snails and mud snails did not exceed Australian and New Zealand Food Standards maximum levels for copper, lead or estimated inorganic arsenic at any site although copper concentrations in oysters and mud snails exceeded generally expected levels at some locations. Bacterial community composition in shellfish was species-specific regardless of location and different to the surrounding water and sediment. In the snails Telescopium telescopium, Terebralia palustris and Nerita balteata, some bacterial taxa differed between sites, but not in Saccostrea cucullata oysters. The abundance of potential human pathogens was very low and pathogen abundance or diversity was not associated with site classification, i.e. sewage impact, industry impact and reference.     

Determination of Heavy Metals in Honey in Kahramanmaraş City, Turkey

Heavy metals in honey are of interest not only for quality control, but also for determination environmental contamination. The objective of this work was to determine distribution of the levels of selected heavy metals. Levels of copper (Cu), cadmium (Cd), manganese (Mn), Iron (Fe), magnesium (Mg) and nickel (Ni) in honey samples (21) in Kahramanmaraş region were determined by atomic absorption spectrometer (AAS). The mean values for Cu, Cd, Mn, Fe, and Mg were 0.01, 0.32, 0.03, 0.36 and 10.45 ppm, respectively. Nickel was not detected in honey samples. Kahramanmaraş honey samples were not free of heavy metals but the levels of them were found well below the permitted levels. The results suggested that honey may be useful for assessing the presence of environmental contaminants.     

Element content of propolis collected from different areas of South Spain

The aim of this work is to determine the content of essential and toxic elements in 25 raw propolis samples, when considering pollution agents and geographical and botanical factors. The microwave-assisted digestion was the most reliable and accurate method for determination of inorganic elements in propolis samples. The results were obtained using certified reference materials in a good agreement with certified values. Inductively coupled plasma atomic emission spectroscopy was used for the determination of 23 macro- and microelements (Ag, Al, As, B, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, and Zn). A Mercury analyzer was also utilized for the detection of the total Hg. Among the analyzed metals, Ca, K, Mg, Zn, Si, S, Fe, Al, P, and Na were found to be the most predominant. Heavy metals (As, Cd, Hg, and Pb) were determined in minimal concentration, and Pb was the highest mean contained toxic (<3.80 mg/kg), without influence on provisional tolerable weekly intake values. The method can be applied for routine analysis and quality and environmental pollution controls of toxic elements in propolis samples. The results obtained indicate no pollution of the collection areas and naturally high concentration of Al (460?±?62.2 mg/kg).     

Determination of heavy metals in bee honey with connected and not connected metal wires using inductively coupled plasma atomic emission spectrometry (ICP–AES)

Two honey samples are taken from two parts of the same honeycomb: one that contacts to the surface of the wire and the other taken from the surface that does not contact the wires. Heavy metal contents of these two samples were determined by inductively coupled plasma atomic emission spectrometry). The Mo, Cd, Cr, Fe, Mn, Ni and Zn contents of the honey in contact with wire is higher when compared to the other. Especially, Fe and Zn contents of honey in contact with wire is much higher than the non-contact one. These values are, respectively, 190.21 and 112.76 ppm. Besides, Ni content of honey in contact with wire is approximately 50% higher.     

Monitoring of trace elements in honey from the Republic of Macedonia by atomic absorption spectrometry

Contents of Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg in 123 honey samples from different regions of the Republic of Macedonia were determined by atomic absorption spectrometry. A microwave digestion system was applied for digestion of the samples. The mean content for the elements determined was found to be: 2.252, 0.696, 1.885, 1.752, 0.004, 29.52, 984.8, 40.11, 18.24 mg kg(-1) for Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg, respectively. Based on a comparison of statistical parameters, the spatial distribution of particular elements in Macedonian honey and the results of factor analysis, two natural and one anthropogenic geochemical associations were identified. The natural geochemical associations (Mg, Mn, Ca, K and Fe, Zn, Ca, -K, -Na) are influenced mainly by lithology. The anthropogenic associations (Cd and -Cu) are mostly a result of metallurgical activities, namely lead production in the town of Veles.     

Determination of some organochlorine pesticide residues in honeys from Konya, Turkey

In this study, 24 organochlorine pesticide residues in 109 different honey samples collected from stores and open markets in Konya, Turkey were analyzed by gas chromatography-electron capture detection. Aldrin, cis-chlordane, trans-chlordane, oxy-chlordane, 2,4^′ -DDE, and 4,4^′ -DDE were found in all honey samples. The mean value was 0.0540 μg g^???1 for oxy-chlordane. In the 55 samples of 109, levels of organochlorine pesticide residues of oxy-chlordane were determined as higher than those of Turkish Alimentarius Codex maximum residual limits (MRLs). Other organochlorine pesticide residues also exceeded MRLs except for cis-heptachlor epoxide and α-hexachlorocyclohexane. Since all of the honey samples are found contaminated and most of these samples exceeded MRLs, a control of organochlorine pesticide residues in honey is necessary for consumer health.     

Determination of traces of copper and zinc in honeys by the solid phase extraction pre-concentration followed by the flame atomic absorption spectrometry detection

A simple and fast solid phase extraction procedure was developed to pre-concentrate traces of Cu and Zn prior to their determination in honey samples by flame atomic absorption spectrometry. The sample preparation included dissolution of honey samples and the passage (at 20 ml/min) of resulting 10 % m/v solutions (100 ml) through Dowex 50W?×?8-400 resin beds in order to quantitatively retain Cu and Zn and separate them from the glucose and fructose matrix. Enriched Cu and Zn traces were recovered with 5.0 ml of a 3.0 mol/l HCl solution and quantified by flame atomic absorption spectrometry. The procedure proposed was used to analyze sixty nine commercially available and freshly ripened honey samples coming from the Lower Silesia region (Poland). It enabled to measure Cu and Zn within the range of 0.01–1.42 and 0.03–15.38 μg/g, respectively, with precision better than 4 %. Accuracy, assessed on the basis of the recovery test and the comparison of results with those obtained using wet digestion and inductively coupled plasma optical emission spectrometry, was ranged from ?4 % to +6 %. Detection limits of Cu and Zn achieved with this method were 5 and 7 ng/g, respectively.     

Examination of honeys and flowers as soil element indicators

Detection of soil element deficiencies is time consuming, requiring a major commitment for field work and analysis. Bees concentrate some elements in their honey which could allow soil element concentrations to be predicted without having to take large numbers of soil samples. We measured 14 element concentrations in soil, sunflower, acacia flower and honey samples from two different regions of Hungary. Across sites, the elements with significant correlation coefficients between honey and soil concentrations, in descending order of probability, were Cu > Ba >Sr = Ni > Zn > Mn = Pb >As. Bioconcentration from soil to honey was similar for areas with acacia and sunflower flowers. In the macroelements, it was the greatest for K, S and P and least for Mg and Na, and in the microelements, greatest for B, then Zn, then Cu, then As, Mo and Sr and least for Fe, Ba, Mn and Pb. It is concluded that in acacia and sunflower-growing regions, honey can give an accurate estimate of soil element concentrations for Cu and Ba and provides relevant information for Sr, Ni, Zn, Mn, Pb and As.     

Ecotoxicological Assessment of the Impact of Residual Heavy Metals on Soil Nematodes in the Guadiamar River Basin (Southern Spain)

On 25 April 1998, as a consequence of the breaking of a dam containing the tailings of a pyrite mine, a land strip of approximately 43 km in length was covered with a layer of black sludge, containing high levels of heavy metals, along the Guadiamar River Basin (southern Spain). In this investigation we carried out an ecotoxicological assessment (field and laboratory studies) of the impact of residual heavy metals (Cu, Pb, Zn, Ni) on soil nematodes in the impacted riparian zone, two years after the huge mine spillage. Concentrations of residual heavy metals were significantly (P<0.05) higher at the impacted sampling sectors (S-2, S-3, S-4, S-5) than at the unpolluted (reference) sampling sector (S-1). Nickel however exhibited the lowest increases at the impacted sectors. As a consequence, correlation coefficients between concentrations of heavy metals and values of ecological indices were not significant for Ni. In contrast, copper, lead and zinc exhibited significant (P<0.05) negative correlation coefficients with ecological indices, particularly with diversity indices (including the~number of taxa). In addition, the toxicity of Cu and Pb to nematode test species (Aphelenchus avenae and Cephalobus persegnis) during short-term toxicity bioassays was much higher than the toxicity of Zn and Ni. We conclude that residual heavy metals were still influencing adversely the community of soil nematodes in the impacted riparian zone of the Guadiamar River Basin. Cu, Pb and, to a lesser extent, Zn would be major responsible for the observed impact.     

Establishing a standard Sonoran Reference Plant and its application in monitoring industrial and urban pollution throughout the Sonoran Desert

Using analyses from honey mesquite (Prosopis glandulosa) leaves from nearly pristine locations in Arizona, an inorganic plant concentration standard is proposed for use as a Sonoran Reference Plant (SRP). Such a standard can be used as a monitoring device for different anthropogenic pollution sources throughout the Sonoran Desert. To test the application of the SRP, honey mesquite leaves were collected at different sites in southern Arizona and their chemical fingerprints compared to SRP. Sources of element origin were identified through factor analysis and correlation matrices. A terrestrial factor was found in leaves from all sites. Anthropogenic factors varied for different sites. Mesquite leaves accumulated significant amounts of elements originating from copper smelters (As, Sb) and urban pollution (La, Sm, Ce, V). These pollutants are small-sized and have been linked to human lung diseases. Mesquite is a deciduous tree; the yearly comparison of mesquite leaf element concentration spectra to the SRP standard can be used to determine seasonal improvement or deterioration of environmental quality in a particular area.     

European bee-eater (Merops apiaster) populations under arsenic and metal stress: evaluation of exposure at a mining site

Two populations of the European bee-eater were studied, one living at a reference site and the other at a metal mining site. The concentration of arsenic and 11 metals (Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn) was measured in feathers and regurgitated pellets collected at both sites. Cadmium, chromium, mercury, nickel, and lead were at least twofold higher in feathers of birds from the contaminated site than in the reference site, suggesting that this population was exposed to higher metal levels. Similarly, levels of aluminum, arsenic, cadmium, cobalt, chromium, iron, and lead were also at least twofold higher in pellets from the contaminated area. The obtained results suggested that the impacted population of Merops apiaster is at risk due to the exposure to some metals.     

Assessments of some metals contamination in lipsticks and their associated health risks to lipstick consumers in Iran

In this study, the concentrations of lead, cadmium, and chromium in lipstick samples were evaluated. The samples were from different brands and produced in different countries. The average lead, cadmium, and chromium concentrations in all lipstick samples were 1.851, 0.017, and 4.300 mg kg^?1 ww, respectively. There was a significant difference in the concentrations of lead, cadmium, and chromium among the brands (p?<?0.05). The concentrations of the measured elements in the brands did not exceed the values of the international standards provided for lipstick. The values of hazard quotient (HQ), health risk index (HI), relative intake index (RII), and estimated daily intake (EDI) indices were calculated. The results of the HQ and HI indices showed that in more than 50% of the lipstick brands, there is a potential threat to consumer health due to the presence of these elements in lipstick. Therefore, it can be concluded that, due to the simultaneous use of lipstick with other types of cosmetics and hence the potential exposure of consumers to toxic elements through all cosmetics, continuous monitoring of the concentrations of these elements in these types of products is necessary to avoid potential health risks.     

Preconcentration and determination of lead and cadmium levels in blood samples of adolescent workers consuming smokeless tobacco products in Pakistan

The present study was aimed to evaluate the cadmium (Cd) and lead (Pb) levels in the blood samples of adolescent boys, chewing different smokeless tobacco (SLT) products in Pakistan. For comparative purpose, boys of the same age group (12–15 years), not consumed any SLT products were selected as referents. To determine trace levels of Cd and Pb in blood samples, a preconcentration method, vortex-assisted liquid–liquid microextraction (VLLME) has been developed, prior to analysis by flame atomic absorption spectrometry. The hydrophobic chelates of Cd and Pb with ammonium pyrrolidinedithiocarbamate were extracted into the fine droplets of ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate, while nonionic surfactant, Triton X-114 was used as a dispersing medium. The main factors affecting the recoveries of Cd and Pb, such as concentration of APDC, centrifugation time, volume of IL and TX-114, were investigated in detail. It was also observed that adolescent boys who consumed different SLT products have 2- to 3-fold higher levels of Cd and Pb in their blood samples as compared to referent boys (p?<?0.001).     

Metal Leachability and Anthropogenic Signal in Roadside Soils Estimated from Sequential Extraction and Stable Lead Isotopes

Several roadside soil samples were collected at two field sites in Sweden. They were analysed for total elemental content (using both ICP-MS and XRF) and stable lead isotopes. Extraction with deicing salt solution and sequential extraction were performed in order to elucidate the potential mobility due to the use of deicing agents. The total concentrations of elements, especially lead, have decreased and lead is presently almost at background concentrations (15-51 ppm for surface samples). However, the isotopic signature indicates that old gasoline lead still is left at the site constructed prior to 1975. The field site constructed in 1992 showed, however, no 206Pb/207Pb ratio below 1.14. Only minor amounts were leached using deicing salt solutions; for lead only 0.29%, on average, was extracted indicating that the mobile fraction already was released. Sequential extraction indicated that lead mainly was associated with reducible (34.4%) and oxidisable (35.4%) fractions. Exchangable and acid soluble fractions contained 20.3% while 10.0% was found in the residual fraction. The salt extraction released, however, very low concentrations indicating that most in fraction 1 is acid soluble (e.g. carbonates). Tungsten was also found at high concentrations indicating a possible impact from studded tires. For tungsten the following composition was obtained: residual (48.0%) > oxidisable (47.6%) > reducible (3.3%) > exchangeable/acid soluble (1.1%). From the isotopic studies it was also suggested that the order for incorporating anthropogenic lead into soils is exchangeable/carbonates > (hydr)oxides > organic matter > residual. The multivariate technique principal component analysis (PCA) seems promising for evaluating large sequential extraction datasets.     

A Prospective Biomonitoring Campaign with Honey Bees in a District of Upper-Bavaria (Germany)

In order to establish a monitoring method to track long term changes of the amount of anthropogenic contamination in a district of Bavaria (Germany), a biomonitoring campaign with honey bees was performed in spring 2002. Expected anomalies from the industry or from residential areas in the sampled district could not be detected. An anomaly over a considerable part of the sampling area correlating with other phenomena lead to the hypothesis of a prehistoric cosmic impact. Moreover a principal component analysis of the data showed evidence for a biogenic, an anthropogenic and an unknown component hypothetically related to a possible cosmic impact.