A comparison of portable XRF and ICP-OES analysis for lead on air filter samples from a lead ore concentrator mill and a lead-acid battery recycler

Personal and area samples for airborne lead were taken at a lead mine concentrator mill, and at a lead-acid battery recycler. Lead is mined as its sulfidic ore, galena, which is often associated with zinc and silver. The ore typically is concentrated, and partially separated, on site by crushing and differential froth flotation of the ore minerals before being sent to a primary smelter. Besides lead, zinc and iron are also present in the airborne dusts, together with insignificant levels of copper and silver, and, in one area, manganese. The disposal of used lead-acid batteries presents environmental issues, and is also a waste of recoverable materials. Recycling operations allow for the recovery of lead, which can then be sold back to battery manufacturers to form a closed loop. At the recycling facility lead is the chief airborne metal, together with minor antimony and tin, but several other metals are generally present in much smaller quantities, including copper, chromium, manganese and cadmium. Samplers used in these studies included the closed-face 37 mm filter cassette (the current US standard method for lead sampling), the 37 mm GSP or "cone" sampler, the 25 mm Institute of Occupational Medicine (IOM) inhalable sampler, the 25 mm Button sampler, and the open-face 25 mm cassette. Mixed cellulose-ester filters were used in all samplers. The filters were analyzed after sampling for their content of the various metals, particularly lead, that could be analyzed by the specific portable X-ray fluorescence (XRF) analyzer under study, and then were extracted with acid and analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES). The 25 mm filters were analyzed using a single XRF reading, while three readings on different parts of the filter were taken from the 37 mm filters. For lead at the mine concentrate mill, all five samplers gave good correlations (r2 > 0.96) between the two analytical methods over the entire range of found lead mass, which encompassed the permissible exposure limit of 150 mg m(-3) enforced in the USA by the Mine Safety and Health Administration (MSHA). Linear regression on the results from most samplers gave almost 1 ratio 1 correlations without additional correction, indicating an absence of matrix effects from the presence of iron and zinc in the samples. An approximately 10% negative bias was found for the slope of the Button sampler regression, in line with other studies, but it did not significantly affect the accuracy as all XRF results from this sampler were within 20% of the corresponding ICP values. As in previous studies, the best results were obtained with the GSP sampler using the average of three readings, with all XRF results within 20% of the corresponding ICP values and a slope close to 1 (0.99). Greater than 95% of XRF results were within 20% of the corresponding ICP values for the closed-face 37 mm cassette using the OSHA algorithm, and the IOM sampler using a sample area of 3.46 cm2. As in previous studies, considerable material was found on the interior walls of all samplers that possess an internal surface for deposition, at approximately the same proportion for all samplers. At the lead-acid battery recycler all five samplers in their optimal configurations gave good correlations (r2 > 0.92) between the two analytical methods over the entire range of found lead mass, which included the permissible exposure limit enforced in the USA by the Occupational Safety and Health Administration (OSHA). Linear regression on the results from most samplers gave almost 1 ratio 1 correlations (except for the Button sampler), indicating an absence of matrix effects from the presence of the smaller quantities of the other metals in the samples. A negative bias was found for the slope of the button sampler regression, in line with other studies. Even though very high concentrations of lead were encountered (up to almost 6 mg m(-3)) no saturation of the detector was observed. Most samplers performed well, with >90% of XRF results within +/- 25% of the corresponding ICP results for the optimum configurations. The OSHA algorithm for the CFC worked best without including the back-up pad with the filter.     

The quality of fiber counts using improved slides with relocatable fields

A parameter based on discrepancies between reported fibers and verified fibers of relocatable slides is shown to be effective in monitoring the quality of airborne fiber counts. Analysts report only the fibers in each field examined. The verified fibers were determined by two experienced analysts, and are here considered as a "true" value. Most of the verified fibers were confirmed by the reported fibers, and the disputed fibers or fiber counting errors were all located and accounted for. In this study, reference (REF) slides were manufactured from proficiency analytical test (PAT) filter samples from the American Industrial Hygiene Association containing chrysotile or amosite. The slides were made using coverglasses bearing a grid pattern to allow accurate re-examinations. These coverglasses are an improved version of those used in previous studies. Seventy-four out of 85 amosite results and 51 out of 60 chrysotile results of REF slides were within their PAT proficiency ranges. When all reported fibers were normalized against their respective verified fibers, the average fiber count was over-estimated for amosite by 38.3% and under-estimated for chrysotile by 30.4%. The error from counting short fibers (sizing-extra) was 82.6% of the extra fibers and accounted for the 38% over-estimation of amosite fibers. For chrysotile fibers, sizing-extra errors were 74.0% of the extra fibers, but by far the larger errors were oversight-missing errors, which were 96.7% of the missing fibers and accounted for the 30% under-estimation of the chrysotile fibers. The discrepancies were found to be linearly related to counting errors as had been noted in a previous study, giving further weight to a proposed score, calculated from the discrepancy parameter (SigmaD(+) + |SigmaD(-)|)/VF(total), for evaluating the proficiencies of analysts. If a proficiency score =60 is selected, 48 out of 85 amosite results and 17 out of 60 chrysotile results satisfied this criterion in this study. The number of fiber counting errors in this study was larger than could be expected by PAT proficiency criteria. It may be useful to complement existing proficiency test programs with these REF slides. At the end of each proficiency testing round, detailed reports of discrepancies can be provided to participants so that they can improve on their skills in searching and sizing fibers and minimize their counting errors. In addition, the internal quality control program of each laboratory could include counting REF slides regularly by all analysts with control charts of (SigmaD(+)/VF(total)), (SigmaD(-)/VF(total)), (SigmaD(+) + |SigmaD(-)|)/VF(total) and RF(total)/VF(total) maintained to monitor errors, proficiencies and intercounter variations. Ten percent of relocatable slides of routine samples could also be recounted to monitor intracounter variation.     

Effectiveness of photocatalytic filter for removing volatile organic compounds in the heating, ventilation, and air conditioning system

Nowadays, the heating, ventilation, and air conditioning (HVAC) system has been an important facility for maintaining indoor air quality. However, the primary function of typical HVAC systems is to control the temperature and humidity of the supply air. Most indoor air pollutants, such as volatile organic compounds (VOCs), cannot be removed by typical HVAC systems. Thus, some air handling units for removing VOCs should be added in typical HVAC systems. Among all of the air cleaning techniques used to remove indoor VOCs, photocatalytic oxidation is an attractive alternative technique for indoor air purification and deodorization. The objective of this research is to investigate the VOC removal efficiency of the photocatalytic filter in a HVAC system. Toluene and formaldehyde were chosen as the target pollutants. The experiments were conducted in a stainless steel chamber equipped with a simplified HVAC system. A mechanical filter coated with Degussa P25 titania photocatalyst and two commercial photocatalytic filters were used as the photocatalytic filters in this simplified HVAC system. The total air change rates were controlled at 0.5, 0.75, 1, 1.25, and 1.5 hr(-1), and the relative humidity (RH) was controlled at 30%, 50%, and 70%. The ultraviolet lamp used was a 4-W, ultraviolet-C (central wavelength at 254 nm) strip light bulb. The first-order decay constant of toluene and formaldehyde found in this study ranged from 0.381 to 1.01 hr(-1) under different total air change rates, from 0.34 to 0.433 hr(-1) under different RH, and from 0.381 to 0.433 hr(-1) for different photocatalytic filters.     

Implications of head and neck restraint test repeatability for specification improvement

Objective: Since 2005, National Association for Stock Car Auto Racing, Incorporated (NASCAR) drivers have been required to use a head and neck restraint system (HNR) that complies with SFI Foundation, Inc. (SFI) 38.1. The primary purpose of the HNR is to control and limit injurious neck loads and head kinematics during frontal and frontal oblique impacts. The SFI 38.1 performance specification was implemented to establish a uniform test procedure and minimum standard for the evaluation of HNRs using dynamic sled testing. The purpose of this study was to evaluate the repeatability of the current SFI 38.1 test setup and explore the effects of a polyester seat belt restraint system.

Method: Eight sled tests were conducted using the SFI 38.1 sled test protocol with additional test setup constraints. Four 0° frontal tests and 4 30° right frontal (RF) oblique tests were conducted. The first 3 tests of each principal direction of force (PDOF) used nylon SFI 16.1 seat belt restraint assemblies. The fourth test of each PDOF used polyester SFI 16.6 seat belt restraint assemblies. A secondary data set (Lab B Data) was also supplied by the HNR manufacturer for further comparisons. The International Organization for Standardization (ISO) 18571 objective comparison method was used to quantify the repeatability of the anthropomorphic test device (ATD) resultant head, chest, and pelvis acceleration and upper neck axial force and flexion extension bending moment time histories across multiple tests.

Results: Two data sets generated using the SFI 38.1 test protocol exhibited large variations in mean ISO scores of ATD channels. The 8 tests conducted with additional setup constraints had significantly lower mean ISO score coefficients of variation (CVs). The Lab B tests conducted within the current specification but without the additional test setup constraints had larger mean ISO score standard deviation and CV for all comparisons. Specifically, tests with the additional setup constraints had average CVs of 3.3 and 2.9% for the 0° and 30° RF orientations, respectively. Lab B tests had average CVs of 22.9 and 24.5%, respectively. Polyester seat belt comparisons had CVs of 5.3 and 6.2% for the 0° and 30° RF orientations, respectively.

Conclusion: With the addition of common test setup constraints, which do not violate the specification, the SFI 38.1 test protocol produced a repeatable test process for determining performance capabilities of HNRs within a single sled lab. A limited study using polyester webbing seat belt assemblies versus the nylon material called for in SFI 38.1 indicates that the material likely has less effects on ATD upper neck axial force and flexion extension bending moment time histories than the test setup freedom currently available within the specification. The additional test setup constraints are discussed and were shown to improve ATD response repeatability for a given HNR.     

Advertisement call duration indicates good genes for offspring feeding rate in gray tree frogs (Hyla versicolor)

Indicator or ”good genes” models of sexual selection predict that mating preferences allow females to choose mates that are genetically superior. Female gray tree frogs (Hyla versicolor) prefer male advertisement calls of long call duration, which can be indicators of enhanced offspring growth performance. We tested the effects of father’s call duration and the presence of a caged predator (dragonfly naiad) on tadpole activity and growth in a factorial experiment, controlling for maternal and environmental effects. The effect of food availability (a repeated measure) on tadpole activity was also examined. Tadpoles responded to predator presence and to high food availability by decreasing activity and feeding. Tadpoles exposed to a caged predator were smaller after 14 days than those exposed to an empty cage, suggesting that spending less time feeding carries the cost of reduced growth. Offspring of males with long versus short calls responded similarly to the presence of a predator. Nonetheless, offspring of long-calling males spent more time feeding than did offspring of short-calling males, except when a predator was present but no food was available. Increased time spent feeding may contribute to enhanced offspring growth and, therefore, to the indirect benefit that a female may realize by selecting a mate with long calls. However, because the behavioral differences depended on the environment, and because the fitness consequences of such behavioral differences should also vary with the environment, the benefit of mating with a long-calling male may depend on the conditions encountered by the offspring. Received: 15 February 2000 / Revised: 24 September 2000 / Accepted: 16 October 2000     

Investigating the chromium status,heavy metal contamination,and ecological risk assessment via tannery waste disposal in sub-Saharan Africa (Kenya and South Africa)

Environmental Science and Pollution Research - To mitigate the negative environmental and public health concerns associated with increased industrial discharges amid the rapid industrial growth,...     

Carbonation of brine impacted fractionated coal fly ash: implications for CO2 sequestration

Coal combustion by-products such as fly ash (FA), brine and CO(2) from coal fired power plants have the potential to impact negatively on the environment. FA and brine can contaminate the soil, surface and ground water through leaching of toxic elements present in their matrices while CO(2) has been identified as a green house gas that contributes significantly towards the global warming effect. Reaction of CO(2) with FA/brine slurry can potentially provide a viable route for CO(2) sequestration via formation of mineral carbonates. Fractionated FA has varying amounts of CaO which not only increases the brine pH but can also be converted into an environmentally benign calcite. Carbonation efficiency of fractionated and brine impacted FA was investigated in this study. Controlled carbonation reactions were carried out in a reactor set-up to evaluate the effect of fractionation on the carbonation efficiency of FA. Chemical and mineralogical characteristics of fresh and carbonated ash were evaluated using XRF, SEM, and XRD. Brine effluents were characterized using ICP-MS and IC. A factorial experimental approach was employed in testing the variables. The 20-150 μm size fraction was observed to have the highest CO(2) sequestration potential of 71.84 kg of CO(2) per ton of FA while the >150 μm particles had the lowest potential of 36.47 kg of CO(2) per ton of FA. Carbonation using brine resulted in higher degree of calcite formation compared to the ultra-pure water carbonated residues.     

Ammonia volatilization from surface-applied poultry litter under conservation tillage management practices

Land application of poultry litter can provide essential plant nutrients for crop production, but ammonia (NH(3)) volatilization from the litter can be detrimental to the environment. A multiseason study was conducted to quantify NH(3) volatilization rates from surface-applied poultry litter under no-till and paraplowed conservation tillage managements. Litter was applied to supply 90 to 140 kg N ha(-1). Evaluation of NH(3) volatilization was determined using gas concentrations and the flux-gradient gas transport technique using the momentum balance transport coefficient. Ammonia fluxes ranged from 3.3 to 24% of the total N applied during the winter and summer, respectively. Ammonia volatilization was rapid immediately after litter application and stopped within 7 to 8 d. Precipitation of 17 mm essentially halted volatilization, probably by transporting litter N into the soil matrix. Application of poultry to conservation-tilled cropland immediately before rainfall events would reduce N losses to the atmosphere but could also increase NO(3) leaching and runoff to streams and rivers.     

Mercury in sediment and fish from North Mississippi Lakes

Sediments and/or fish were collected from Sardis, Enid and Grenada Lakes, which are located in three different watersheds in North Mississippi, in order to assess mercury contamination. The mean total mercury concentration in sediments from Enid Lake in 1997 was 0.154 mg Hg/kg, while 1998 sediment concentrations in Sardis, Enid and Grenada Lakes were 0.112, 0.088 and 0.133 mg Hg/kg, respectively. Sediment mercury concentrations in 1999 were similar in all three lakes but, generally lower than 1998. Mean total mercury concentrations in edible fillets of fish collected from Enid Lake in 1998 were above the human health FDA action level (>1.0 mg Hg/kg) for bass (1.40), crappie (1.69) and gar (1.89); however, tissue concentrations were less than 1.0 mg Hg/kg in carp (0.63) and catfish (0.82). Human hazard indexes for each species was 1 for both adults and children, indicating that there is a potential for toxic effects to occur. In addition, calculated consumption limits indicate that adults may consume 4–12 oz. of fish per month, depending on the species consumed. For children, 2 oz. per month may be consumed. Further studies are needed to determine the exact environmental consequences and human health impacts associated with mercury contamination in North Mississippi and the Southeastern United States.     

Physical impact of waterjet‐based sediment remediation on benthic organisms

Adding activated carbon to sediments has been shown to be an effective means of reducing the bioavailability of certain contaminants. The current state of the practice is to mechanically mix activated carbon to a target concentration of 3 percent at depths of approximately 30 cm using a rotovator or similar construction equipment. Waterjets have been used to cut hard material using a mixture of water and an abrasive. If activated carbon is substituted for the abrasive, waterjets have the potential to use surface injection as a replacement for mechanical mixing during sediment remediation. A perceived benefit of waterjet‐based sediment remediation is that there may be a reduced potential for benthic organism mortality related to amendment delivery. A set of waterjet parameters were identified that have the potential to achieve amendment placement goals, and a series of waterjet tests were conducted to evaluate the potential impact on the benthic community. The tests included mortality testing using a swimming macroinvertebrate and a burrowing invertebrate, benthic artifacts such as shells, and craft foam as a surrogate for living organisms. The results indicated that the immediate survivability was typically greater than 50 percent, and that empirical relationships between two variables (waterjet nozzle diameter and the water column height between the nozzle and the target) and the depth of cut in the foam could be established. Data are not available in the literature for direct comparison of organism survivability immediately after mechanical mixing, but the results of this study provide motivation for the further evaluation of waterjets on the basis of the low observed mortality rates. Future waterjet work may address field‐scale characterization of mixing effectiveness, resuspension potential, technical feasibility, and cost. © 2011 Wiley Periodicals, Inc.