Air exposure assessment and biological monitoring of manganese and other major welding fume components in welders

In a cross-sectional study, 96 welders were compared with 96 control subjects. Also 27 former welders, all diagnosed as having manganism, were examined. Exposure to welding fumes was determined in the 96 welders, while the concentration of elements in whole blood and urine was determined in all subjects. The geometric mean (GM) concentrations of manganese (Mn) and iron in the workroom air were 97 microg m(-3) (range 3-4620 microg m(-3); n=188) and 894 microg m(-3) (range 106-20 300 microg m(-3); n=188), respectively. Thus the Mn concentration in the workroom air was on average 10.6% (GM) of that of the Fe concentration. No substantial difference was observed in the air Mn concentrations when welding mild steel as compared to welding stainless steel. The arithmetic mean (AM) concentration of Mn in whole blood (B-Mn) was about 25% higher in the welders compared to the controls (8.6 vs. 6.9 microg l(-1); p < 0.001), while the difference in the urinary Mn concentrations did not attain statistical significance. A Pearson's correlation coefficient of 0.31 (p < 0.01) was calculated between B-Mn and Mn in the workroom air that was collected the day before blood sampling. Although the exposure to welding fumes in the patients had ceased on average 5.8 years prior to the study (range 4 years-7 years), their AM B-Mn concentration was still higher than in referents of similar age (8.7 microg l(-1) vs. 7.0 microg l(-1)). However, their urinary concentrations of cobolt, iron and Mn were all statistically significantly lower.     

Corrosion-induced release of the main alloying constituents of manganese-chromium stainless steels in different media

The main focus of this paper is the assessment of release rates of chromium, nickel, iron and manganese from manganese-chromium stainless steel grades of low nickel content. The manganese content varied between 9.7 and 1.5 wt% and the corresponding nickel content between 1 and 5 wt%. All grades were exposed to artificial rain and two were immersed in a synthetic body fluid of similar pH but of different composition and exposure conditions. Surface compositional studies were performed using X-ray photoelectron spectroscopy (XPS) in parallel to correlate the metal release process with changes in surface oxide properties. All grades, independent of media, revealed a time-dependent metal release process with a preferential low release of iron and manganese compared to nickel and chromium while the chromium content of the surface oxide increased slightly. Manganese was detected in the surface oxide of all grades, except the grade of the lowest manganese bulk content. No nickel was observed in the outermost surface oxide. Stainless steel grades of the lowest chromium content (approximately 16 wt%) and highest manganese content (approximately 7-9 wt%), released the highest quantity of alloy constituents in total, and vice versa. No correlation was observed between the release rate of manganese and the alloy composition. Released main alloy constituents were neither proportional to the bulk alloy composition nor to the surface oxide composition.     

Evaluation of metal contents of household detergent samples from Turkey by flame atomic absorption spectrometry

The concentrations of cadmium, copper, chromium, cobalt, iron, lead, manganese, nickel, and zinc in detergent samples from Kayseri, Turkey were determined by flame atomic absorption spectrometry. HClO₄ (10 mL)/HNO₃ (10 mL) mixture was used for the digestion of household detergent samples. The correctness of the analytical procedures was checked with standard addition–recovery tests in different detergent samples for the investigated metal ions. The concentration ranges of the elements in the detergent samples were found as 17.2–60.1, 11.1–40.1, 2.5–32.3, 8.1–10.5, 7.2–21.6, 9.8–17.9, 1.7–3.8, 12.5–22.5, and 2.0–5.8 μg/g for iron, manganese, zinc, copper, lead, cobalt, cadmium, nickel, and chromium, respectively. The values found in this work were compared with some other studies around the world conducted on detergent samples.     

Dispersion and bioaccumulation of elements from an open-pit olivine mine in Southwest Greenland assessed using lichens, seaweeds, mussels and fish

This study investigated dispersion and bioaccumulation of mining-related elements from an open-pit olivine mine at Seqi in Southwest Greenland (64°?N) using lichens (Flavocetraria nivalis), seaweeds (Fucus vesiculosus), mussels (Mytilus edulis) and fish (Myoxocephalus scorpius). The mine operated between 2005 and 2009, and samples were taken every year within a monitoring area 0–17 km from the mine during the period 2004–2011. A total of 46 elements were analysed in the samples. After mining began, highly elevated metal concentrations, especially nickel (Ni), chromium (Cr), iron (Fe) and cobalt (Co), were observed in lichens relative to pre-mining levels (up to a factor of 130) caused by dust dispersion from the mining activity. Elevated metal concentrations could be measured in lichens in distances up to ~5 km from the mine/ore treatment facility. Moderately elevated concentrations of Ni and Cr (up to a factor of 7) were also observed in seaweeds and mussels but only in close vicinity (<1 km) to the mine. Analyses of fish showed no significant changes in element composition. After mine closure, the elevated metal concentrations in lichens, seaweeds and mussels decreased markedly, and in 2011, significantly elevated metal concentrations could only be measured in lichens and only within a distance of 1 km from the mine.     

Metal Accumulation by Riverine and Lacustrine Populations of Angulyagra Oxytropis (Benson) (Gastropoda : Viviparidae)

Cadmium, chromium, iron, manganese, nickel, lead and zinc concentrations were determined in sediment and body tissues, viz. digestive gland, mantle and shell, of the freshwater snail, Angulyagra oxytropis (Benson) (Gastropoda : Viviparidae), from River Barak and one of its floodplain lakes in Cachar district, Assam State, Northeastern India. The concentrations of all the metals except iron are significantly higher in the lake sediment. When compared to their riverine counterparts, the lacustrine snails contain higher concentrations of cadmium, chromium and iron in their mantle; nickel and zinc in digestive gland; manganese in both digestive gland and mantle; and lead in all the three tissues examined. The accumulation patterns of most of the metals varied considerably between the two sites. The implications of these findings in storage, sequestration and detoxification of metals by this animal are discussed. The study also indicates that A. oxytropis may be a potential biological indicator of metal contamination in freshwater ecosystems.     

Variability in concentrations of potentially toxic elements in urban parks from six European cities

Use of a harmonised sampling regime has allowed comparison of concentrations of copper, chromium, nickel, lead and zinc in six urban parks located in different European cities differing markedly in their climate and industrial history. Wide concentrations ranges were found for copper, lead and zinc at most sites, but for chromium and nickel a wide range was only seen in the Italian park, where levels were also considerably greater than in other soils. As might be expected, the soils from older cities with a legacy of heavy manufacturing industry (Glasgow, Torino) were richest in potentially toxic elements (PTEs); soils from Ljubljana, Sevilla and Uppsala had intermediate metal contents, and soils from the most recently established park, in the least industrialised city (Aveiro), displayed lowest concentrations. When principal component analysis was applied to the data, associations were revealed between pH and organic carbon content; and between all five PTEs. When pH and organic carbon content were excluded from the PCA, a distinction became clear between copper, lead and zinc (the "urban" metals) on the one hand, and chromium and nickel on the other. Similar results were obtained for the surface (0-10 cm depth) and sub-surface (10-20 cm depth) samples. Comparisons with target or limit concentrations were limited by the existence of different legislation in different countries and the fact that few guidelines deal specifically with public-access urban soils intended for recreational use.     

Trace metal levels and some chemical parameters in herby cheese collected from south eastern Anatolia-Turkey

Due to the consumption of the herby cheese in south eastern Anatolia-Turkey is at high ratio, chemical parameters such as dry matter, pH, acidity, aCl, protein, fat and trace metal contents in 50 different herby cheeses produced at this region have been determined in the presented study. The content of lead, copper, cobalt, nickel, chromium, cadmium, and iron have been analyzed by flame atomic absorption spectrometer in air/acetylene flame after combination ash digestion method and wet digestion method. The mean concentration of lead, copper, cobalt, nickel, chromium and cadmium in our samples are higher than literature values except iron.     

Metal release rate from AISI 316L stainless steel and pure Fe, Cr and Ni into a synthetic biological medium--a comparison

Metal release rates from stainless steel grade 316L were investigated in artificial lysosomal fluid (ALF), simulating a human inflammatory cell response. The main focus was placed on release rates of main alloying elements using graphite furnace atomic absorption spectroscopy, and changes in surface oxide composition by means of X-ray photoelectron spectroscopy. To emphasise that alloys and pure metals possess totally different intrinsic properties, comparative studies were performed on the pure alloying constituents: iron, nickel and chromium. Significant differences in release rates were observed due to the presence of a passive surface film on stainless steel. Iron and nickel were released at rates more than 300 times lower from the 316L alloy compared with the pure metals whereas the release rate of chromium was similar. Iron was preferentially released compared with nickel and chromium. Immersion in ALF resulted in the gradual enrichment of chromium in the surface film, a small increase of nickel, and the reduction of oxidized iron with decreasing release rates of alloy constituents as a result. As expected, released metals from stainless steel grade 316L were neither in proportion to the bulk alloy composition nor to the surface film composition.     

Metals in tissues of fish from Yelkoma Lagoon, northeastern Mediterranean

This study was performed to investigate the metal concentrations in muscle, liver, gonad, and gill of gilthead seabream (Sparus aurata L., 1758), European seabass (Dicentrarchus labrax L., 1758), and keeled mullet (Liza carinata Valenciennes, 1836) from Yelkoma Lagoon, northeastern Mediterranean region. So, the levels of cadmium, cobalt, chromium, copper, iron, manganese, nickel, lead, and zinc in tissues of specimens from the lagoon were determined by inductively coupled plasma optical emission spectrometer. Concentrations of metals in muscles of the examined species ranged from 0.10 to 0.47 mg kg^???1 for cadmium, 0.10 to 0.43 mg kg^???1 for cobalt, 0.17 to 0.72 mg kg^???1 for chromium, 0.62 to 1.03 mg kg^???1 for copper, 28.9 to 52.3 mg kg^???1 for iron, 0.75 to 0.96 mg kg^???1 for manganese, 0.11 to 0.57 mg kg^???1 for nickel, 0.19 to 0.47 mg kg^???1 for lead, and 6.01 to 13.9 mg kg^???1 for zinc, respectively. Additionally, metal concentrations in muscles of fish were assessed for human uses according to provisional tolerable weekly intake and provisional tolerable daily intake.     

Unanticipated potential cancer risk near metal recycling facilities

Metal recycling is an important growing industry. Prior to this study, area sources consisting of metal recycling facilities fell in a category of limited regulatory scrutiny because of assumed low levels of annual emissions. Initiating with community complaints of nuisance from smoke, dust and odor, the Houston Department of Health and Human Services (HDHHS) began a monitoring program outside metal recycler facilities and found metal particulates in outdoor ambient air at levels which could pose a carcinogenic human health risk. In a study of five similar metal recycler facilities which used a torch cutting process, air downwind and outside the facility was sampled for eight hours between 6 and 10 times each over 18 months using a mobile laboratory. Ten background locations were also sampled. Iron, manganese, copper, chromium, nickel, lead, cobalt, cadmium and mercury were detected downwind of the metal recyclers at frequencies ranging from 100% of the time for iron to 2% of the time for mercury. Of these metals, chromium, nickel, lead, cobalt, cadmium and mercury were not detected in any sample in the background. Two pairs of samples were analyzed for total chromium and hexavalent chromium to establish a ratio of the fraction of hexavalent chromium in total chromium. This fraction was used to estimate hexavalent chromium at all locations. The carcinogenic risk posed to a residential receptor from metal particulate matter concentrations in the ambient air attributed to the metal recyclers was estimated from each of the five facilities in an effort to rank the importance of this source and inform the need for further investigation. The total risk from these area sources ranged from an increased cancer risk of 1 in 1,000,000 to 6 in 10,000 using the 95th upper confidence limit of the mean of the carcinogenic metal particulate matter concentration, assuming the point of the exposure is the sample location for a residential receptor after accounting for wind direction and the number of shifts that could operate a year. Further study is warranted to better understand the metal air pollution levels in the community and if necessary, to evaluate the feasibility of emission controls and identify operational improvements and best management practices for this industry.This research adds two new aspects to the literature: identification of types and magnitude of metal particulate matter air pollutants associated with a previously unrecognized area source, metal recyclers and their potential risk to health.     

Seasonal and spatial distribution of trace elements in the water and sediments of the Tsurumi River in Japan

The Tsurumi, a class-one Japanese river, has a significant metal loading originating from urban environment. Water and sediment samples were collected from 20 sites in winter and summer, 2009 and were analyzed to determine and compare the extent of different trace element enrichment. A widely used five-step sequential extraction procedure was also employed for the fractionation of the trace elements. Concentrations of zinc, copper, lead, chromium, and cadmium were three to four times higher than that of reference values and downstream sediments are much more polluted than the upstream sites. Geochemical partitioning results suggest that the potential trace metal mobility in aquatic environment was in the order of: cadmium > zinc > lead > copper > cobalt > chromium > molybdenum > nickel. About 80.2% zinc, 77.9% molybdenum, 75.3% cobalt, 63.7% lead, 60.9% copper, 55.1% chromium, and 39.8% nickel in the sediment were contributed anthropogenically. According to intensity of pollution, Tsurumi river sediments are moderately to heavily contaminated by zinc, lead, and cobalt. Enrichment factor values demonstrated that zinc, lead, and molybdenum have minor enrichment in both the season. The pollution load index (PLI) has been used to access the pollution load of different sampling sites. The area load index and average PLI values of the river were 7.77 and 4.93 in winter and 7.72 and 4.89 in summer, respectively. If the magnitude of pollution with trace metal in the river system increases continuously, it may have a severe impact on the river’s aquatic ecology.     

Energy-dispersive X-ray fluorescence analysis of moss and soil from abandoned mining of Pb-Zn ores

This research investigates heavy metal pollution around one of the most important mining areas in Turkey, the Sebinkarahisar (Giresun) lead–zinc mining, by means of analyzing moss and soil samples collected in the neighborhood of the copper mining at different distances. Energy dispersive X-ray fluorescence spectrometry (Epsilon 5, PANalytical, Almelo, The Netherlands) is utilized in the experiments. The results have indicated that the both moss and soil samples contain aluminum, vanadium, chromium, manganese, iron, nickel, copper, zinc, arsenic, barium, cerium, tungsten, and lead. The comparison of the heavy metal concentrations with the typical measurements in the world and with the limit values for the human health has revealed the critical heavy metal pollution levels in the region. The possible consequences of these results are briefly discussed from the point of potential hazards to ecology and human health.     

Metal concentrations in eight fish species from Aegean and Mediterranean Seas

The concentrations of cadmium, cobalt, chromium, copper, iron, manganese, nickel, lead, and zinc were determined by ICP-AES in muscles and livers of eight fish species sampled from the Aegean and Mediterranean seas of Turkey. Iron showed the highest levels, followed by Zinc in examined tissues of all fish species. Metal concentrations in edible parts of fish species were 0.03–0.37 mg kg^???1 for cadmium, 0.02–0.42 mg kg^???1 for cobalt, 0.15–1.78 mg kg^???1 for chromium, 0.17–1.11 mg kg^???1 for copper, 11.0–33.4 mg kg^???1 for iron, 0.02–0.89 mg kg^???1 for manganese, 0.22–4.03 mg kg^???1 for nickel, 0.22–0.64 mg kg^???1 for lead, and 2.88–10.9 mg kg^???1 for zinc, respectively. All metal concentrations in livers were higher than those in muscles. In some stations, cadmium, chromium, cobalt, and lead concentrations in both muscles and livers of the examined species were higher than permissible safety levels for human uses.     

密闭微波消解 ICP- AES 法测定大气颗粒物中金属元素

采用过氯乙烯滤膜采集、密闭微波消解、电感耦合等离子发射光谱法测定大气颗粒物中铅、镍、铬、铜、铁、锌、锰、钡、镉,优化了试验条件.方法线性良好,各元素的检出限在0.001 mg/L～0.01 mg/L之间,滤膜样品测定的RSD为0.6%～2.9%,加标回收率为96.0%～105%.     

Trace metals content in soils along the state road 51 (northeastern Poland)

The aim of the study was to determine concentrations of some trace elements (lead, cadmium, chromium, and nickel) in soils along State Road 51 leading from Olsztyn to Olsztynek, northeastern Poland. The traffic flow had a significant effect on the content of heavy metals in soils lying along the road. Further away from the road, and under a lower traffic flow intensity, the amounts of contaminants originating from the motor traffic decreased. There was a pine forest growing by the road near Olsztyn, which served as a buffer zone for all the analyzed heavy metals. At all the sampling locations, the content of chromium was approximately the same as its natural concentration. The statistical analysis demonstrated that there was a strong negative correlation between the concentrations of nickel, lead, chromium, and cadmium in soils and the distance from the road. The biggest differences in the content of an individual element were determined for lead and the smallest ones—for cadmium. Emissions of trace elements depended on the differences in the traffic flow intensity, number, type, and speed of vehicles and on the atmospheric conditions as well as the distribution of buildings.     

Heavy metals and selenium in feathers of three shorebird species from Delaware bay

Concentrations of lead, cadmium, mercury, selenium, chromium and manganese were examined in breast feathers of shorebirds migrating north through Cape May, New Jersey in 1991 and 1992. Although we predicted that metal levels would be positively correlated with weight, this was only true for mercury in red knots (Calidris canutus). Selenium was negatively correlated with weight in red knots. No other significant correlation of metal concentrations with weight were found. Lead and mercury were highest in sanderlings (C. alba). Selenium and manganese were highest in red knots, while chromium and cadmium levels were highest in semipalmated sandpipers (C. pusilus). For 1991, interspecific metals differences were significant for all metals except lead. For semipalmated sandpipers, cadmium and chromium concentrations were significantly higher in 1991 while managese concentrations were significantly higher in 1992.     

Trace Element Concentrations in Fish, Surficial Sediments and Water from Northern Part of the Persian Gulf

Concentrations of cadmium, lead, nickel and vanadium were determined in water, surficial sediments and the muscle of three demersal fish species (Epinephelus coioides, Psettodes erumei and Solea elongate) from 15 sampling sites in the northern part of Persian Gulf. Concentrations of the elements were determined using Inductively Coupled Plasma Mass Spectrometer. There were no significant differences among the sampling sites in Cd and Pb levels in the sediments. The highest concentrations of Ni and V in sediments were found near the southern coast of Qeshm Iland and Bandar Lengeh. Concentrations of Cd, Pb and Ni in the sediments were notably higher than global baseline values. Nearly in all cases the element concentrations in the sediments were considerably greater than RSA (ROPME Sea Area) and the ERL (Effects Range Low) guidelines. Significant differences among the sampling sites could be found for concentrations of all the four metals in water. The mean Ni, Pb and Cd levels in the water samples were relatively higher than those in some other regions of the Persian Gulf. Except few cases, the mean concentrations of the elements in muscle of the selected fish species were markedly below the international guidelines for human consumption.     

Distribution and partitioning of iron, zinc, and arsenic in surface sediments in the Grande River mouth to Cuitzeo Lake, Mexico

Cuitzeo Lake is one of the largest and most important lakes in Mexico. It receives different types of pollutants through its main tributary, the Grande River of Morelia. The aim of this work was to determine if high concentrations of iron, zinc, and arsenic are present in sediments in an area near the river mouth to the lake, as well as to estimate the partitioning of these metals using a sequential extraction procedure in order to obtain information of their potential bioavailability. Sediment samples were collected from three different sites in Cuitzeo Lake and two sites in Grande River in both dry and wet seasons. A sequential extraction procedure was carried out to determine the concentrations of these elements in different geochemical phases of the sediments. Total metal concentrations were evaluated by using the enrichment factor and the geoaccumulation index. A comparison with sediment quality guidelines and shale values has also been made. The results indicate that sediments are considered unpolluted by iron and moderately polluted by zinc and arsenic. However, fractionation studies showed that significant amounts of Zn and As could be released to the lake ecosystem depending on the environmental conditions, representing a medium risk potential of bioavailability to the biota.     

Welding fumes from stainless steel gas metal arc processes contain multiple manganese chemical species

Fumes from a group of gas metal arc welding (GMAW) processes used on stainless steel were generated using three different metal transfer modes and four different shield gases. The objective was to identify and measure manganese (Mn) species in the fumes, and identify processes that are minimal generators of Mn species. The robotic welding system was operated in short-circuit (SC) mode (Ar/CO2 and He/Ar), axial spray (AXS) mode (Ar/O2 and Ar/CO2), and pulsed axial-spray (PAXS) mode (Ar/O2). The fumes were analyzed for Mn by a sequential extraction process followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis, and by X-ray diffraction (XRD). Total elemental Mn, iron (Fe), chromium (Cr) and nickel (Ni) were separately measured after aqua regia digestion and ICP-AES analysis. Soluble Mn2+, Fe2+, Fe3+, and Ni2+ in a simple biological buffer (phosphate-buffered saline) were determined at pH 7.2 and 5.0 after 2 h incubation at 37 C by ion chromatography. Results indicate that Mn was present in soluble form, acid-soluble form, and acid-soluble form after reduction by hydroxylamine, which represents soluble Mn0 and Mn2+ compounds, other Mn2+ compounds, and (Mn3+ and Mn4+) compounds, respectively. The dominant fraction was the acid-soluble Mn2+ fraction, but results varied with the process and shield gas. Soluble Mn mass percent in the fume ranged from 0.2 to 0.9%, acid-soluble Mn2+ compounds ranged from 2.6 to 9.3%, and acid plus reducing agent-soluble (Mn3+ and Mn4+) compounds ranged from 0.6 to 5.1%. Total Mn composition ranged from 7 to 15%. XRD results showed fumes had a crystalline content of 90-99% Fe3O4, and showed evidence of multiple Mn oxides, but overlaps and weak signals limited identification. Small amounts of the Mn2+ in the fume (<0.01 to ≈ 1% or <0.1 to ≈ 10 microg ml(-1)) and Ni2+ (<0.01 to ≈ 0.2% or <0.1 to ≈ 2 mg ml(-1)) ions were found in biological buffer media, but amounts were highly dependent on pH and the welding process. Mn generation rates for the fractions were tabulated, and the influence of ozone is discussed. The conclusions are that exposures to welding fumes include multiple Mn species, both soluble and insoluble, and that exposures to Mn species vary with specific processes and shield gases.     

Assessment of radionuclide and metal contamination in a thorium rich area in Norway

The Fen Central Complex in southern Norway, a geologically well investigated area of magmatic carbonatite rocks, is assumed to be among the world largest natural reservoirs of thorium ((232)Th). These rocks, also rich in iron (Fe), niobium (Nb), uranium ((238)U) and rare earth elements (REE), were mined in several past centuries. Waste locations, giving rise to enhanced levels of both radionuclides and metals, are now situated in the area. Estimation of radionuclide and metal contamination of the environment and radiological risk assessment were done in this study. The average outdoor gamma dose rate measured in Fen, 2.71 μGy h(-1), was significantly higher than the world average dose rate of 0.059 μGy h(-1). The annual exposure dose from terrestrial gamma radiation, related to outdoor occupancy, was in the range 0.18-9.82 mSv. The total activity concentrations of (232)Th and (238)U in soil ranged from 69 to 6581 and from 49 to 130 Bq kg(-1), respectively. Enhanced concentrations were also identified for metals, arsenic (As), lead (Pb), chromium (Cr) and zinc (Zn), in the vicinity of former mining sites. Both radionuclide and heavy metal concentrations suggested leaching, mobilization and distribution from rocks into the soil. Correlation analysis indicated different origins for (232)Th and (238)U, but same or similar for (232)Th and metals As, Cr, Zn, nickel (Ni) and cadmium (Cd). The results from in situ size fractionation of water demonstrated radionuclides predominately present as colloids and low molecular mass (LMM) species, being potentially mobile and available for uptake in aquatic organisms of Norsj? Lake. Transfer factors, calculated for different plant species, showed the highest radionuclide accumulation in mosses and lichens. Uptake in trees was, as expected, lower. Relationship analysis of (232)Th and (238)U concentrations in moss and soil samples showed a significant positive linear correlation.