X-ray diffraction spectrometric analysis of nickel refinery aerosols,process materials and particulates isolated from worker lung tissues

Results are reported of X-ray diffraction analysis of extracts derived from lungs of two nickel refinery workers and of three stationary air samples collected inside a nickel refinery. Since environmental samples from the 1950s and 1960s do not exist, two archived production control samples from that period were also analyzed. Because nickel has been found in respiratory tissue of workers retired for more than twenty years, it was likely that the residual nickel compounds must be rather insoluble. Preliminary surveys showed that sulfur was not present in the lung tissue deposits and thus water-soluble and sulfidic nickel were therefore extracted from the ten process samples before the X-ray analysis. A common compound that was found in all 10 samples was trevorite. This is a spinel-type mineral, much like magnetite where the divalent iron is replaced by nickel. It may be formed when trivalent iron reacts with nickel at 1100 degrees C. It has magnetic properties and is very insoluble. Samples from the lungs were obtained by burning off the organic tissue at 630 degrees C. Due to a relatively high detection limit for the X-ray diffraction technique, we were initially not able to detect any mineral nickel compound. But when particles extracted with a magnet were analyzed, a very clear diffraction pattern of trevorite was identified. The main residue after the magnetic separation had a low concentration of nickel (4 microg g(-1)), which suggests that trevorite was the dominating, if not the only, nickel compound present. In addition, chemical analyses were performed on 13 tissue samples from one single lung; one from each main bronchus, two from each lobe, and an additional one from the lower right lobe. Statistical testing showed a highly significant correlation between the five elements determined: Ni, Co, Cu, Fe and Cr. This suggests that these metals are isomorphous and substitute for each other in the mineral structure. These results may indicate that the nickel left in the lungs some years after exposure is trevorite, and may be biologically inert. However, further speciation of nickel compounds in the lungs seems warranted, and trevorite should be tested for its potential toxic effects.     

Prediction of the solubility of zinc, copper, nickel, cadmium, and lead in metal-contaminated soils

Risk assessment of metal-contaminated soil depends on how precisely one can predict the solubility of metals in soils. Responses of plants and soil organisms to metal toxicity are explained by the variation in free metal ion activity in soil pore water. This study was undertaken to predict the free ion activity of Zn, Cu, Ni, Cd, and Pb in metal-contaminated soil as a function of pH, soil organic carbon, and extractable metal content. For this purpose, 21 surface soil samples (0–15 cm) were collected from agricultural lands of various locations receiving sewage sludge and industrial effluents for a long period. One soil sample was also collected from agricultural land which has been under intensive cropping and receiving irrigation through tube well water. Soil samples were varied widely in respect of physicochemical properties including metal content. Total Zn, Cu, Ni, Cd, and Pb in experimental soils were 2,015?±?3,373, 236?±?286, 103?±?192, 29.8?±?6.04, and 141?±?270 mg kg^?1, respectively. Free metal ion activity, viz., pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺, as estimated by the Baker soil test was 9.37?±?1.89, 13.1?±?1.96, 12.8?±?1.89, 11.9?±?2.00, and 11.6?±?1.52, respectively. Free metal ion activity was predicted by pH-dependent Freundlich equation (solubility model) as a function of pH, organic carbon, and extractable metal. Results indicate that solubility model as a function of pH, Walkley–Black carbon (WBC), and ethylenediaminetetraacetic acid (EDTA)-extractable metals could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺ to the extent of 59, 56, 46, 52, and 51 %, respectively. Predictability of the solubility model based on pH, KMnO₄-oxidizable carbon, and diethylenetriaminepentaacetic acid-extractable or CaCl₂-extractable metal was inferior compared to that based on EDTA-extractable metals and WBC.     

The changing nature of the 206Pb/207Pb isotopic ratio of lead in rainwater, atmospheric particulates, pine needles and leaded petrol in Scotland, 1982-1998

The inductively coupled plasma-mass spectrometry (ICP-MS)-determined 206Pb/207Pb ratio of 145 samples of rainwater collected at 25 locations around Scotland during December 1997 and January 1998 and at three longterm monitoring stations in the northeast, central belt and southeast of the country from November 1997 to December 1998 averaged 1.144+/-0.017 (1 s). This represents a significant increase from the mean value of 1.120+/-0.016 recorded for the long-term sites in 1989 1991, only partly attributable to a concomitant increase in the 206Pb/207Pb ratio of leaded petrol from 1.075+/-0.013 to 1.088+/-0.007. The rainwater 206Pb/207Pb data for the late 1990s also contrast markedly with the lower 206Pb/207Pb ratios found for pine needle and atmospheric particulate samples from Scotland (e.g. Glasgow: 1.085+/-0.012 in 1985-1986, 1.099+/-0.007 in 1991-1992), England and Western Europe in this study for the period 1982-1992 when emissions of lead to the atmosphere from petrol-engined vehicles in the UK were approximately 2-9 times higher. The observed change in the lead isotopic signature of rainwater predominantly reflects the impact of measures, such as the introduction and growing uptake of unleaded petrol, to reduce car exhaust emissions of lead to the atmosphere in the UK. Based on the rainwater data, source apportionment calculations suggest a general decline in the contribution of leaded petrol to atmospheric lead in Scotland from 53-61% in 1989-1991 to 32-45% in 1997-1998, with a corresponding decline in the urban environment from 84-86% to 48-58%.     

Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

Chemistry of fogs at Agra, India: Influence of soil particulates and atmospheric gases

Fog water samples were collected in the months of December and January during 1998–2000 at Agra, India. The samples were analyzed for pH, major anions (F⁻, Cl⁻, SO₄ ²⁻, NO₃ ⁻, HCOO⁻ and CH₃COO⁻), major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺) and NH₄ ⁺ using ion chromatography, ICP-AES and spectrophotometer methods, respectively. pH of fog water samples ranged between 7.0 and 7.6 with a volume weighted mean of 7.2, indicating its alkaline characteristic. NH₄ ⁺ contributed 40%, SO₄ ²⁻ and NO₃ ⁻ accounted for 28%, while Ca²⁺, Mg²⁺, Na⁺ and K⁺ accounted for 16% of the total ionic concentration. The ratios of Mg²⁺/Ca²⁺ and Na⁺/Ca²⁺ in fog water indicates that 50–75% of fog water samples correspond to the respective ratios in local soil. Significant correlation between Ca²⁺, Mg²⁺, Na⁺ and K⁺ suggests their soil origin. The order of neutralization, NH₄ ⁺ (1.4) > Ca²⁺ (0.28) > Mg²⁺ (0.12), indicates that NH₄ ⁺ is the major neutralizing species. Fog water and atmospheric alkalinity were also computed and were found to be 873 and 903 neqm⁻³, respectively. Both of these values are higher than values reported from temperate sites and thus indicate that at the present level of pollutants, there is no risk of acid fog problem. The study also shows that the alkaline nature of fog water is due to dissolution of ammonia gas and partly due to interaction of fog water with soil derived aerosols.     

Assessment of lead, zinc, copper, nickel and chromium in total suspended particulate matter from the workplace in Al-Rusayl Industrial Estate, Oman

Total suspended particulates (TSP) were collected with a high volume sampler from the indoor work environment of 23 industries in Al-Rusayl Industrial Estate in Muscat, Oman. The values measured ranged from 39 microg m(-3) to 1033 microg m(-3). TSP in the ambient air of the area was found to have an average value of 1802 microg m(-3). TSP were analyzed for Pb, Cu, Ni, Zn and Cr. Compared to other metals, Pb emission was high with values ranging from 3 to 15 109 ng m(-3) with the mean value being 1 293 ng m(-3); Cu concentration varied from 3 to 2600 ng m(-3) with a mean value of 131 ng m(-3); Ni concentration ranged from 6 to 46 ng m(-3) with a mean value of 17 ng m(-3); Cr concentration ranged from 1 to 133 ng m(-3) with a mean value of 23 ng m(-3) while that of Zn varied from 0.01 to 1 978 ng m(-3) with the mean value being 464 ng m(-3). The concentrations of Pb, Ni, Cu, Cr, and Zn in the ambient air were also measured and found to have the following values: 122, 18, 16, 5 and 0.01 ng m(-3), respectively. These values indicate that the industries in the area do not contribute significantly to heavy metal air pollution.     

Determination of nickel, copper, zinc and lead in human scalp hair in Syrian occupationally exposed workers by total reflection X-ray fluorescence

In this study, an attempt has been made to study methane flux and quantification of heavy metals from Municipal Solid Waste (MSW) landfill areas of selected cities in India. During the period of study, the average value of methane flux was estimated from these landfill areas varied from 146–454 mg/m2/h. Methane emission from landfill is of serious environmental global concern as it accounts for approximately 15 percentages of current Greenhouse gas emissions. It has been estimated that methane emission, from landfill areas in the world, in next two decades would be same as that what is emitted from paddy fields presently. Besides, the estimation of methane flux, quantification of some heavy metals was conducted to analyse the suitability of using MSW as compost. The average values for metals were observed to be both within the range of USEPA and Indian standards for MSW disposal in landfill areas and to be used as compost respectively.     

强酸型离子交换纤维富集-火焰原子吸收测定水中痕量铜、铅、镉、镍

通过强酸型离子交换纤维柱,在同一水样中同时富集和洗脱了铜、铅、镉、镍,采用火焰原子吸收光谱法测定,并对富集条件及洗脱条件、干扰因素进行了探讨。该方法简便易行,回收率在96.1%~105.5%之间,测定的相对标准偏差小于5.0%。     

Analysis of cadmium, nickel, and lead in commercial moist and dry snuff used in Pakistan

The extent to which smokeless tobacco endangers human health is an ongoing subject of debate. In this study, concentrations of toxic metals, cadmium (Cd), lead (Pb), and nickel (Ni), were measured in different snuff products (dry brown and black and moist green and brown), available and consumed in Pakistan. Concentrations of Cd, Pb, and Ni were determined in 23 samples of various brands of snuff by electrothermal atomic absorption spectrometry, after microwave-assisted acid digestion. The reliability of methodology was assured by analyzing certified reference material. The resulted data of toxic metals in different snuff products are comparable to the existing information with limited exceptions. It was estimated that 10 g intake of different types of snuff could contribute 14–68, 17–47, and 20–73 % of the provisional maximum tolerable daily intake for Cd, Ni, and Pb, respectively.     

Permeability of hair to cadmium,copper and lead in five species of terrestrial mammals and implications in biomonitoring

The capacity of mammal hair to absorb toxic metals and its utility in biomonitoring has been broadly studied. Though these metal-binding properties has generally been attributed to the sulphur contained in cysteine, an amino acid that forms part of keratin, there are not many experimental studies that analyze the role of sulphur in the external deposition of potentially toxic metallic elements in order to better understand the potential of hair in biomonitoring and generate better tools for differentiating between internal and external deposition of contaminants. In this study, an experimental analysis is carried out using a scanning electron microscope on hairs of five terrestrial mammal species (Peromyscus furvus, P. maniculatus, Glossophaga soricina, Artibeus jamaicensis and Marmosa mexicana) treated with cadmium, copper and lead salts. We quantified absorbed metals as well as natural elements of the hair by energy dispersive X-ray spectroscopy (EDS) to analyze using simple statistics the role of sulphur in the absorption Cd, Cu and Pb. Given the lack of studies comparing the mechanisms of deposition of metal elements among different orders of Class Mammalia, external morphology was considered to be an important factor in the deposition of metallic particles of Cd, Cu and Pb. Bat species (Glossophaga soricina, Artibeus jamaicensis) showed a high concentration of particles in their scales, however, no between-species differences in metal absorption were observed, and during the exogenous deposition metal particles do not permeate the medulla. These results suggest that the sulphur in hair itself cannot bind metals to hair cuticle and that hair absorption capacity depends on a variety of factors such as aspects of hair morphology.     

Determination of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey

The concentrations of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey were investigated. Soil samples were collected at distances of 0, 25 and 50 m from the roadside. The concentrations of lead, cadmium and copper were measured by Flame Atomic Absorption Spectrophotometry (FAAS). A slotted tube atom trap (STAT) was used to increase the sensitivity of lead and cadmium in FAAS. Lead concentrations in soil samples varied from 1.3 to 45 mg kg⁻¹ while mean lead levels in plants ranged from120 ng g⁻¹ for grape in point-4 to 866 ng g⁻¹ for apple leaves in point-2. Lead analyses showed that there was a considerable contamination in both soil and plants affected from traffic intensity. Overall level of Cd in soil samples lies between 78 and 527 ng/g while cadmium concentration in different vegetations varied in the range of 0.8–98.0 ng g⁻¹. Concentrations of copper in soil and plant samples were found in the range of 11.1–27.9 mg kg⁻¹ for soil and 0.8–5.6 mg kg⁻¹ for plants. Standard reference material (SRM) was used to find the accuracy of the results of soil analyses.     

Microscopic and chemical studies of metal particulates in tree bark and attic dust: evidence for historical atmospheric smelter emissions, Humberside, UK

Tree barks and attic dusts were examined as historical archives of smelter emissions, with the aim of elucidating the pathways of pollution associated with a plume of Sn and Pb contamination in top soils, found close to the former Capper Pass smelter, Humberside, UK. Samples were collected from three villages within the area of the contamination plume. Scanning electron microscopy (SEM) and bulk chemical analyses were used to assess particle type, number and deposition patterns. SEM analysis of dusts and bark revealed that Sn and Pb particles were present in samples from all three villages along with copper, zinc and iron particles. These were almost entirely <10 microm in diameter and occurred mostly as oxides, frequently forming clusters of sub-micron crystals. Samples further from the smelter contained considerably fewer particles. We present images of smelter derived Sn particles. Chemical assays of the barks and attic dusts demonstrated that concentrations of Sn, Pb, Cu, As, Sb and Cd diminished with increasing distance from the source. Strong positive correlations were found between Sn and Pb, As, Sb and Cd in the attic dusts. Enrichment factors (EF) were calculated for these trace elements based on topsoil element concentrations obtained from the soil survey of the study area. Decreases in these trace element concentrations and EF values with distance away from the smelter are consistent with trends found in the soil survey for Sn and Pb and are typical of deposition patterns around smelter stacks. The study demonstrates that tree bark and attic dusts can be effective archives of metal particulates deposited from large static emission sources.     

The use of artificial neural networks to forecast biological atmospheric allergens or pathogens only as Alternaria spores

The monitoring of atmospheric Alternaria spores is of major importance due to their adverse effects on crops and their role as human allergens. Most species act as plant pathogens, prompting considerable economic losses worldwide on important crops such as potato, tomato or wheat. Fungal spores can also have serious detrimental effects on human health, triggering respiratory diseases and allergenic processes. The aim of this study was not only to examine the relationship between the atmospheric Alternaria spore content and the prevailing meteorological parameters, but also to predict the atmospheric Alternaria spore content in the Northwest Spain using a novel data analysis technique, ANNs (Artificial Neural Networks). A Hirst-type LANZONI VPPS 2000 volumetric 7-day recording sampler was used to collect the airborne spores from 1997 to 2008. Neural networks provided us with a good tool for forecasting Alternaria airborne spore concentration, and thus could help the automation of the prediction system in the aerobiological information diffusion to the population suffering from allergic problems or the prevention of considerable economic worldwide losses on important crops. Our proposed model would be applied to different geographical areas; nevertheless, the adjustment of the model, by using the available and adequate variables, would be realised in each case.     

Cadmium, copper, lead, and zinc in Mugil cephalus from seven coastal lagoons of NW Mexico

The increasing order of the mean concentrations of Cd, Cu, and Zn in the tissues of Mugil cephalus of seven coastal lagoons of Sinaloa State (NW Mexico) was liver > gills > muscle, while for Pb it was gills > muscle ≥ liver. There were no differences between the mean concentrations of Cd and Pb of the three tissues determined in the samples of the seven lagoons and, although there were some significant differences, there was no indication of a latitude-related trend in the distribution of Cu and Zn: the Cu content of the muscle tended to be higher in the northern than in the southern lagoons, although in the case of the gills the highest and lowest mean values indicated an opposite trend, with the highest and lowest values in one southern and one northern lagoon. In the case of the liver, there were no differences and no indication of a regional trend. There were no differences in the mean Zn contents of muscle and gills; in the case of the liver, one of the lagoons of the central part of the state had a significantly higher value than one of the southern lagoons and all the rest had similar values. In addition, there was no clear indication of season-related differences in any of the three tissues. According to our results, the metal contents of the muscle of this species are not of concern for human health, since the allowable ingestion would be in the order of 0.9 kg/day.     

Environmental hazard of cadmium, copper, lead and zinc in metal-contaminated soils remediated by sulfosuccinamate formulation

Accumulation of metals in soil at elevated concentrations causes risks to the environmental quality and human health for more than one hundred million people globally. The rate of metal release and the alteration of metal distribution in soil phases after soil washing with a sulfosuccinamate surfactant solution (Aerosol 22) were evaluated for four contaminated soils. Furthermore, a sequential extraction scheme was carried out using selective extractants (HAcO, NH(2)OH·HCl, H(2)O(2) + NH(4)AcO) to evaluate which metal species are extracted by A22 and the alteration in metal distribution upon surfactant-washing. Efficiency of A22 to remove metals varied among soils. The washing treatment released up to 50% of Cd, 40% of Cu, 20% of Pb and 12% of Zn, mainly from the soluble and reducible soil fractions, therefore, greatly reducing the fraction of metals readily available in soil. Metal speciation analysis for the solutions collected upon soil washing with Aerosol 22 further confirmed these results. Copper and lead in solution were mostly present as soluble complexes, while Cd and Zn were present as free ions. Besides, redistribution of metals in soil was observed upon washing. The ratios of Zn strongly retained in the soil matrix and Cd complexed with organic ligands increased. Lead was mobilized to more weakly retained forms, which indicates a high bioavailability of the remaining Pb in soil after washing. Comprehensive knowledge on chemical forms of metals present in soil allows a feasible assessment of the environmental impact of metals for a given scenario, as well as possible alteration of environmental conditions, and a valuable prediction for potential leaching and groundwater contamination.     

Multi-component assessment of worker exposures in a copper refinery. Part 2. Biological exposure indices for copper, nickel and cobalt

Urinary copper (Cu), nickel (Ni) and cobalt (Co) concentrations were determined for 127 Cu refinery workers (40 females, 87 males), with values of the 95% upper confidence interval of the geometric mean in nmol per mmol creatinine of 89 (Ni), 42 (Cu) and 3.4 (Co) for electrorefinery workers. In the pyrometallurgical departments, the corresponding concentrations were 37 (Ni), 99 (Cu) and 11 (Co). Female workers had higher Co urinary concentrations than males (p< or = 0.05) while no gender difference was observed for Cu and Ni. Inter-elemental correlations were moderate to weak. Based on the inhalable aerosol levels reported previously for the same workers, the observed urinary Cu concentrations were considerably lower than expected, relative to Co and Ni. This is interpreted in terms of the current understanding of Cu homeostasis.     

Cadmium,zinc, lead,and copper in livers and kidneys of cattle in the neighbourhood of zinc refineries

Cattle in the Kempen area (in the province North-Brabant, the Netherlands) were investigated for cadmium, lead, zinc, and copper in livers and kidneys. The animals originated from farms located within a 20 km radius around several zinc refinery plants. The local soil is polluted with zinc and cadmium because of a thermal refining process used in the past.Mean cadmium organ concentrations were 2.5 times, and mean lead organ concentrations were 1.5 times higher than the concentrations found in controls. Copper levels tended to be decreased, but zinc levels did not differ from controls.The observed cadmium and lead organ concentrations did not indicate intoxication of the animals, but 22% of the kidneys and 3% of the livers investigated trespassed the maximum tolerance limit of cadmium with regard to human consumption.Continuous control of cadmium organ contents in organs from slaughtercattle kept in cadmium-polluted areas is recommended.     

Cu、Pb、Zn火焰原子吸收多谱线分析在环境监测中的应用

对铜的 3条谱线 (2 49.2 nm、2 61 .4nm,3 2 4.8nm ) ,铅的 2条谱线 (2 83 .3 nm、2 1 7.0 1 nm )以及锌的 2条谱线(3 0 7.6nm、2 1 3 .9nm ) ,共 7条谱线的灵敏度、检测限、线性范围进行了归纳性总结 ,并对多种共存元素可能存在的干扰情况进行了研究 ,认为利用元素不同分析谱线的分析灵敏度差异 ,根据被测元素在样品消解液中含量 ,选择合适的谱线进行分析 ,既降低工作强度 ,又能获得满意结果