Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

A comparison of methods and materials for the analysis of leaded wipes

The purposes of this study are: (1) to determine whether proficiency analytical test (PAT) materials from the American Industrial Hygiene Association can be used to provide quality data for portable X-ray fluorescence analysis (XRF) of lead in dust wipe surface samples; (2) to provide data to determine whether the on-site analysis of field dust wipe samples by XRF and the laboratory method of inductively coupled plasma emission analysis (ICP) are comparable; and (3) to determine if differences exist between different wipe materials. Several wipes meet the ASTM E1792 performance requirements of lead background level less than 5 microg per wipe, be only one layer thick, yield recovery rates of 80- 120% from spiked samples, remain damp throughout the sampling procedure, and do not contain aloe. The wipes used in this study were Pace Wipes, which are used for the PAT materials, and, for the field samples, Palintest Wipes, which were supplied by the instrument manufacturer, and Ghost Wipes, which are popular because they digest in hot, concentrated acid, so that chemical analysis is simplified. Twenty PAT wipe samples were obtained from four different proficiency test rounds. Surface wipe samples were taken at three different locations representing different industry types. All samples were analyzed using a portable XRF spectrometer and by ICP. Strong linear relationships were found for the analysis of wipe samples by ICP and by portable XRF. For the PAT samples, the results from the ICP and XRF analysis were not statistically equivalent, which indicates a bias in the ICP analysis. The bias was not excessive, since all ICP analyses fell within the acceptable range for the proficiency samples. The good correlation between the proficiency sample reference values and the XRF determinations is not surprising considering similar proficiency samples were used to calibrate the instrument response. Users of this portable XRF analyzer could enroll in the proficiency test program as part of their quality assurance program. For field samples, the relationship was strongest for Palintest wipes, and the values found for all three industries could be combined. However, the results from the ICP and XRF analysis were not statistically equivalent using the correction factor in the calculation algorithm as supplied with the instrument, and a new coefficient was derived. The mean relative error for the XRF analysis versus the ICP analysis was greater than 25%, such that the method falls within the realm of screening procedures. For Ghost Wipe samples, the precision was different for different industries, and the results could not be pooled. Differences between the two wipe materials may be related to the number of folds required for analysis.     

Arsenic-speciation in arsenate-resistant and non-resistant populations of the earthworm,Lumbricus rubellus

Arsenic speciation was determined in Lumbricus rubellus Hoffmeister from arsenic-contaminated mine spoil sites and an uncontaminated site using HPLC-MS, HPLC-ICP-MS and XAS. It was previously demonstrated that L. rubellus from mine soils were more arsenate resistant than from the uncontaminated site and we wished to investigate if arsenic speciation had a role in this resistance. Earthworms from contaminated sites had considerably higher arsenic body burdens (maximum 1,358 mg As kg-1) compared to the uncontaminated site (maximum 13 mg As kg-1). The only organo-arsenic species found in methanol/water extracts for all earthworm populations was arsenobetaine, quantified using both HPLC-MS and HPLC-ICP-MS. Arsenobetaine concentrations were high in L. rubellus from the uncontaminated site when concentrations were expressed as a percentage of the total arsenic burden (23% mean), but earthworms from the contaminated sites with relatively low arsenic burdens also had these high levels of arsenobetaine (17% mean). As arsenic body burden increased, the percentage of arsenobetaine present decreased in a dose dependent manner, although its absolute concentration rose with increasing arsenic burden. The origin of this arsenobetaine is discussed. XAS analysis of arsenic mine L. rubellus showed that arsenic was primarily present as As(III) co-ordinated with sulfur (30% approx.), with some As(v) with oxygen (5%). Spectra for As(III) complexed with glutathione gave a very good fit to the spectra obtained for the earthworms, suggesting a role for sulfur co-ordination in arsenic metabolism at higher earthworm arsenic burdens. It is also possible that the disintegration of As(III)-S complexes may have taken place due to (a) processing of the sample, (b) storage of the extract or (c) HPLC anion exchange. HPLC-ICP-MS analysis of methanol extracts showed the presence of arsenite and arsenate, suggesting that these sulfur complexes disintegrate on extraction. The role of arsenic speciation in the resistance of L. rubellus to arsenate is considered.     

Socioeconomic Factors Affecting Farmers’ Perceptions of Land Degradation and Stonewall Terraces in Central Palestine

Land degradation by soil erosion is a socioeconomic and environmental problem facing many developing countries. Application of stonewall terraces for soil moisture conservation is vital to reducing the environmental impacts of this phenomenon. To this end, a field plot experiment was conducted in the study area along with the use of a closed-ended questionnaire. The object of the experiment was to study the socioeconomic impacts of soil erosion on local farmers and their adoption of the stonewall terrace technique. The study showed a higher net profit in areas that had implemented terrace conservation practices than in areas that had not (i.e., 3.5 to 6 times higher net profit). Correlation analysis indicated that the farmers’ perceptions, land ownership, and geomorphology were significantly related to the farmers’ incentives and willingness to adopt terraces as soil conservation measures (P < 0.05), although the correlations were negative. Smallholder farmers (52% of the interviewed farmers) were involved in the sale of the agricultural land for urban uses, largely because of the high price and immediate returns offered. However, the associated land use changes warrant greater involvement of both the private and public sectors. This cooperation may be accomplished through the introduction of a long-term agricultural loan system and the development of proper legislation accompanied by a comprehensive and durable infrastructure and service system with the goal of reducing the negative impact of land use changes and encouraging sustainable use of resources.     

Trace-level beryllium analysis in the laboratory and in the field: state of the art, challenges and opportunities

Control of workplace exposure to beryllium is a growing issue in the United States and other nations. As the health risks associated with low-level exposure to beryllium are better understood, the need increases for improved analytical techniques both in the laboratory and in the field. These techniques also require a greater degree of standardization to permit reliable comparison of data obtained from different locations and at different times. Analysis of low-level beryllium samples, in the form of air filters or surface wipes, is frequently required for workplace monitoring or to provide data to support decision-making on implementation of exposure controls. In the United States and the United Kingdom, the current permissible exposure level is 2 microg m(-3) (air) and the United States Department of Energy has implemented an action level of 0.2 microg m(-3) (air) and 0.2 microg/100 cm(2) (surface). These low-level samples present a number of analytical challenges, including (1) a lack of suitable standard reference materials, (2) unknown robustness of sample preparation techniques, (3) interferences during analysis, (4) sensitivity (sufficiently low detection limits), (5) specificity (beryllium speciation) and (6) data comparability among laboratories. Additionally, there is a need for portable, real-time (or near real-time) equipment for beryllium air monitoring and surface wipe analysis that is both laboratory-validated and field-validated in a manner that would be accepted by national and/or international standards organizations. This paper provides a review of the current analytical requirements for trace-level beryllium analysis for worker protection and also addresses issues that may change those requirements. The current analytical state of the art and relevant challenges facing the analytical community will be presented, followed by suggested criteria for real-time monitoring equipment. Recognizing and addressing these challenges will present opportunities for laboratories, research and development organizations, instrument manufacturers and others.     

Determination of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) by ICP-OES and their speciation in Algerian Mediterranean Sea sediments after a five-stage sequential extraction procedure

Surface sediment samples (n = 18) were collected from the Algerian Mediterranean coasts and analyzed for seven metals using inductively coupled plasma-optical emission spectrometry in order to asses the distribution and bioavailability of metals and to study the anthropogenic factors affecting their concentrations. Sediment samples were size-fractionated into three sizes: 1,080–500 (coarse), 500–250 (medium), and <250 mm (fine). Bulk sediments were subjected to both sequential extraction and total digestion to evaluate the reliability of the sequential extraction procedure (SEP), while the fractions have been only sequentially extracted for metals speciation. The metals were sequentially extracted into five phases namely exchangeable (P1), carbonates (P2), Fe–Mn oxides (P3), organic (P4) and residual (P5). Metal recoveries in sequential extractions were ±20% of the independently measured total metal concentrations; the high recovery rates indicate the good reliability of the SEP used in this study. Correlation coefficients indicated that the grain size has an effect on the distribution of metals in the investigated samples. The order of metal levels in the fractions was medium > fine > coarse for all the metals. The average total extractable metal concentrations for Cd, Cr, Cu, Fe, Ni, Pb, and Zn were 1.1, 8.8, 4.7, 1,291.3, 13.9, 5.7 and 20.4 μg/g, respectively. The northeastern shelf had the lowest metal levels while the highest were in northwestern part mainly due to the significant tourism activities in the northwestern part. Comparison of our results to Earth’s crust values and to previous studies points out that our samples were relatively unpolluted with respect to the heavy metals investigated; most of the metals are not from anthropogenic sources. Enrichment factors as the criteria for examining the impact of the anthropogenic sources of heavy metals were calculated, and it was observed that the investigated samples were not contaminated with Cr, Cu, and Fe, moderately contaminated with Ni, Pb, and Cd, and contaminated with Cd in some sites. The P5 phase had the highest percents of Cr, Cu, Fe, Ni, and Zn. Cadmium and lead were predominant in the P4 phase, while Cu, Fe and Zn were distributed in the order P5 > P3 > P4 > P2 > P1. The following order of bioavailability was found with the heavy metals Pb > Cr > Cd > Ni > Zn > Cu > Fe.     

Total Mercury Distribution in Different Tissues of Frigate Tuna (Auxis thazard thazard) from the Atlantic Coastal Waters of Ghana, Gulf of Guinea

Total mercury concentrations in different tissues of frigate tuna fish (Auxis thazard thazard) was determined by the cold vapour atomic absorption spectrometry technique using an automatic mercury analyzer. A mixture of HNO₃, HClO₄ and H₂SO₄ was used for complete oxidation of organic tissue. The concentration of mercury obtained was in the order Gills < Stomach < Gonads < Intestine < Heart < Duodenum < Liver < Muscle. The concentration of total mercury detected in the edible muscle tissue of the tuna fish tested ranged from 0.044 to 0.201 μg g⁻¹ (mean = 0.108 μg g⁻¹) wet weight. These levels are all within the maximum allowed/recommended level in fish (0.5 μg g⁻¹ wet weight) set by the Food and Agriculture Organisation/World Health Organisation (FAO/WHO) and are therefore unlikely to constitute any significant mercury exposure to the general population because of consumption of tuna fish. The results of the study suggest a relatively clean marine environment that has not been significantly impacted by mercury contamination probably due to minimal industrial activity in the region.     

Intra- and intercompartmental associations between levels of organochlorines in maternal plasma, cord plasma and breast milk, and lead and cadmium in whole blood, for indigenous peoples of Chukotka, Russia

Long-range transport of pollutants towards circumpolar regions emphasizes the need for up-to-date and reliable biological monitoring data. This paper explores the use, reliability and availability of maternal blood (MB) and plasma (MP), cord blood (CB) and plasma (CP) and mother's milk (MM) in terms of assessing exposure to persistent toxic substances (PTSs). It is concluded that MP has the best combination of availability, sensitivity in terms of number of PTSs, their detection frequency and concentrations, and physiological relevance. The study group consisted of 48 pregnant women of indigenous origin from the Chuchki district in the eastern Russian arctic. Blood, CB and MM specimens were collected from all women and MP, CP and MM were analyzed for the Arctic Monitoring and Assessment Programme (AMAP) suite of organochlorines (OCs) and metals (Pb and Cd in MB and CB). Generally speaking, the levels of PTSs coincided with those indicated in several AMAP publications from Chukotka and other areas of northern Russia. The correlations of PTS concentrations between the three body fluid compartments exceeded the minimum statistical requirements of alpha = 0.05 and beta = 0.20 for most of the compounds, with r > 0.46 except for Cd (r = 0.05); lipid adjustments for the OCs did not affect the r-values to any significant extent. The majority of the inter-OC correlations within compartments also fulfilled the indicated statistical condition. Careful consideration is given to the replacement of concentrations below the detection limit, OC detection frequency, the criteria for log-transformation of the data, analytical uncertainty, and biological variability. Practical implications of the findings are explored.     

Sewage pollution effects on mesozooplankton structure in a shallow temperate estuary

The effects of a sewage effluent with no treatment on the mesozooplankton structure and the environmental quality were evaluated in the Bahía Blanca Estuary, during June to November 1995. The highest values of particulate organic matter, nutrients and specially phosphate, were observed in the effluent discharge zone. In addition, taxa richness, mesozooplankton abundance and Shannon diversity values were lower in the sewage discharge area compared with the less polluted area. Eurytemora americana and Acartia tonsa as well as larvae of Balanus glandula, Neohelice granulata and Spionidae were found in the discharge area with lower densities. These results highlight the importance of sewage effluent effects on mesozooplankton community providing background data to use in other monitoring programmes.     

Can fish gill anomalies be used to assess water quality in freshwater Neotropical systems?

Gill anomalies in two fish species (Geophagus brasiliensis and Astyanax bimaculatus) were compared among three freshwater systems with different water quality: one eutrophic river, one eutrophic reservoir, and one oligotrophic reservoir. The raised hypotheses are that reservoirs with low water quality (eutrophic) have fish with more gills anomalies compared with reservoirs with high water quality (oligotrophic), and that the more stable environmental conditions of eutrophic rivers have fish with better healthy conditions than eutrophic reservoirs that have lesser stable environmental conditions. Gills of 36 adult individuals of G. brasiliensis and 23 of A. bimaculatus collected during the winter 2008 and winter 2009 were examined, and the proportions of occurrence of nine histological alterations were compared for the two species among the three systems using a binomial t test for independent samples. Histological changes in fish gills that are reversible and unspecific, such as epithelial lifting, interstitial edema, leukocyte infiltration, hyperplasia of the epithelial cells, lamellar fusion, and vasodilatation were common in both fish species in the three systems. However, lamellar aneurism, which is a more serious and often irreversible anomaly, and lamellar blood congestion occurred only in fish from the two reservoirs. Alternatively, necrosis occurred more in fish from the river. Fish gill anomalies in both species did not differ between the two reservoirs, despite having different water quality. We rejected the hypothesis that reservoirs with lower water quality have fish with more gill injuries compared with high water quality reservoirs. Moreover, the eutrophic river seems to affect differently the healthy condition of fish species, compared with the eutrophic reservoir.