A comparison of X-ray fluorescence and wet chemical analysis of air filter samples from a scrap lead smelting operation

Personal and area air samples were taken at a scrap lead smelter operation in a bullet manufacturing facility. Samples were taken using the 37-mm styrene-acrylonitrile closed-face filter cassette (CFC, the current US standard device for lead sampling), the 37-mm GSP or "cone" sampler, the 25-mm Institute of Occupational Medicine (IOM) inhalable sampler, and the 25-mm Button sampler (developed at the University of Cincinnati). Polyvinylchloride filters were used for sampling. The filters were pre- and post-weighed, and analyzed for lead content using a field-portable X-ray fluorescence (XRF) analyzer. The filters were then extracted with dilute nitric acid in an ultrasonic extraction bath and the solutions were analyzed by inductively coupled plasma optical emission spectroscopy. 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. The single reading from the 25-mm filters was adjusted for the nominal area of the filter to obtain the mass loading, while the three readings from the 37-mm filters were inserted into two different algorithms for calculating the mass loadings, and the algorithms were compared. The IOM sampler was designed for material collected in the body of the sampler to be part of the collected sample as well as that on the filter. Therefore, the IOM sampler cassettes were rinsed separately to determine if wall-loss corrections were necessary. All four samplers gave very good correlations between the two analytical methods above the limit of detection of the XRF procedure. The limit of detection for the 25-mm filters (5 microg) was lower than for the 37-mm filters (10 microg). The percentage of XRF results that were within 25% of the corresponding ICP results was evaluated. In addition, the bias from linear regression was estimated. Linear regression for the Button sampler and the IOM sampler using single readings and the GSP using all tested techniques for total filter loading gave acceptable XRF readings at loadings equivalent to sampling at the OSHA 8-hour Action Level and Permissible Exposure Limit. However, the CFC only had acceptable results when the center reading corrected for filter area was used, which was surprising, and may be a result of a limited data set. In addition to linear regression, simple estimation of bias indicated reasonable agreements between XRF and ICP results for single XRF readings on the Button sampler filters, (82% of the individual results within criterion), and on the IOM sampler filters (77% or 61%--see text), and on the GSP sampler filters using the OSHA algorithm (78%). As a result of this pilot project, all three samplers were considered suitable for inclusion in further field research studies.     

The fate of fipronil in modular estuarine mesocosms

The degradation and corresponding product manifold for the pesticide fipronil was determined in three replicate estuarine mesocosms. Aqueous fipronil concentrations rapidly decreased over the 672 h timescale of the experiment (95% removal). Loss was apparently first-order in fipronil, although there appeared to be a change in the removal mechanism after 96 h that corresponded to a dramatic slowdown in its disappearance. The reduction product of fipronil, fipronil sulfide, was not detected in the water column; however, it formed rapidly in sediments and was identified as the major product of fipronil degradation in the system (20% yield at 672 h, with respect to initial fipronil concentration). Fipronil sulfone is thought to form primarily via biological oxidation; and, although it was generated rapidly in the water column (10% yield), only trace amounts were detected in the sediment (1% yield). The direct photolysis product of fipronil, fipronil desulfinyl, was present in all samples; it formed rapidly in the water column (4% yield) and partitioned into the sediment phase (7% yield) over the course of the experiment. The mass balance on fipronil and associated products was 42% at 672 h.     

A pilot project to detect and forecast harmful algal blooms in the northern Gulf of Mexico

More timely access to data and information on the initiation, evolution and effects of harmful algal blooms can reduce adverse impacts on valued natural resources and human health. To achieve this in the northern Gulf of Mexico, a pilot project was initiated to develop a user-driven, end-to-end (measurements to applications) observing system. A key strategy of the project is to coordinate existing state, federal and academic programs at an unprecedented level of collaboration and partnership. Resource managers charged with protection of public health and aquatic resources require immediate notice of algal events and a forecast of when, where and what adverse effects will likely occur. Further, managers require integrated analyses and interpretations, rather than raw data, to make effective decisions. Consequently, a functional observing system must collect and transform diverse measurements into usable forecasts. Data needed to support development of forecasts will include such properties as sea surface temperature, winds, currents and waves; precipitation and freshwater flows with related discharges of sediment and nutrients; salinity, dissolved oxygen, and chlorophyll concentrations (in vivo fluorescence); and remotely-sensed spatial images of sea surface chlorophyll concentrations. These data will be provided via a mixture of discrete and autonomous in situ sensing with near real-time data telemetry, and remote sensing from space (SeaWiFS), aircraft (hyperspectral imagery) or land (high-frequency radar). With calibration across these platforms, the project will ultimately provide a 4-dimensional visualization of harmful algae events in a time frame suitable to resource managers.     

Trihalomethanes in Drinking Water of Greater Québec Region (Canada): Occurrence, Variations and Modelling

The levels of trihalomethanes (THMs) – the main species of by-product from water chlorination – were monitored in thedistribution systems of the five major drinking water utilitiesof the greater area of Québec City in order to investigate andmodel their occurrence on a spatial and seasonal basis. Data forTHMs and other water quality and operational parametersassociated with their formation were generated through a 16 monthsampling program involving several sites representing variablewater residence times, from the plant to the system extremity.The results demonstrate that the differences in measured THMlevels between the five utilities are mainly due to the variablequality of raw waters, the type of water treatment process beingused and the type and levels of applied disinfectant. Dependingon the utility, average THM levels were from 1.3 to 2.5 timeshigher in the system extremities than in the water leaving thetreatment plant. Also, average levels of THMs measured in summerat the distribution system extremities were, depending on theutility, from 2.5 to 5 times higher than the average levelsmeasured in winter. The seasonal differences were found to besignificantly greater than those observed by others in waterutilities in the United States and Europe and are explained inlarge part by the considerable changes, over the year, in thequality and temperature of surface waters in Southern Québec. Forthe five utilities under study, multivariate regression modelswere developed in order to predict spatial and seasonalvariations of THMs. Both residual chlorine demand and temperaturewere found to be better, statistically, as predictors for THMoccurrence. The usefulness of the developed models for routineand long term water quality management, as well as for assessmentof human exposure to THMs, are also discussed.     

Concentrations and profiles of polychlorinated biphenyls, -dibenzo-p-dioxins and -dibenzofurans in livers of mink from South Carolina and Louisiana,U.S.A

In South Carolina, U.S.A., mink have been reintroduced from two apparently healthy populations to areas where populations haveexisted in the past but have been extirpated. High mortality wasobserved during transport of mink from the source populations. Inorder to elucidate the potential effects of dioxin-like compoundson the survival and reproduction of mink, concentrations of totalpolychlorinated biphenyls (PCBs), p,p-DDE, dioxin-likePCBs, polychlorinated dibenzo-p-dioxins (PCDDs), anddibenzofurans (PCDFs) were measured in livers of mink collectedfrom the source populations in South Carolina and Louisiana. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxinequivalents (TEQs) for the South Carolina and Louisiana mink were21 and 14 pg g^-1, wet wt., respectively. PCB and TEQ concentrations were close to the threshold values that can, under laboratory conditions, elicit toxic effects in ranchmink. Therefore, any additional exposures of these populations toTEQs might adversely affect their populations.     

Induction of cytochrome P4501A and endocrine disrupting effects of school incinerator residues

The emission of the dioxin-like compounds from on-site waste incinerators of seven schools in Kyonggi Province of Korea was evaluated by determination of the cytochrome P4501A(CYP1A) catalytic activity and antiestrogenic activity using cell culturemicrobioassay. The residue samples were extracted in a Soxhlet apparatus using toluene for 20 hr. The concentrated crude extractswere fractionated with a basic alumina column. Dioxin-like compounds were then extracted. Induction of CYP1A activity in a rat(H4IIE) hepatoma cell line was used as indicator of biologicaleffect of incinerator residues and measured as 7-ethoxyresorufin-O-deethylase(EROD) activities. The EROD activities of fraction II extracts (one of the two extracts) in the H4IIE cells were from 0.044±0.002 to 4.424±0.351 ng-TEQ g^-1 (TCDD Toxicity equivalent), showing relatively high inducing capacity. Antisetrogenicity of the extracts was measured as decrease in E₂-induced cell proliferation. Most of the extracts showed antiestrogenic activity in MCF7-BUS cell.The TEQ levels of the incinerator residues and the antiestrogenicactivities were in good correlation, strongly suggesting that thepotent toxic emissions were indeed produced from the on-site school waste semi-incinerators and could cause the antiestrogenicity.     

Incorporating natural capital into economy-wide impact analysis: a case study from Alberta

Traditionally, decision-makers have relied on economic impactestimates derived from conventional economy-wide models. Conventional models lack the environmental linkages necessary for examining environmental stewardship and economic sustainability, and in particular the ability to assess the impact of policies on natural capital. This study investigatesenvironmentally extended economic impact estimation on a regionalscale using a case study region in the province of Alberta knownas the Foothills Model Forest (FMF). Conventional economic impactmodels are environmentally extended in pursuit of enhancingpolicy analysis and local decision-making. It is found that theflexibility of the computable general equilibrium (CGE) modelingapproach offers potential for environmental extension, with a solid grounding in economic theory. The CGE approach may be the tool of the future for more complete integrated environment andeconomic impact assessment.     

Comparison of Two Manual Methods of Nitrogen Dioxide Determination in Ambient Air

Sodium arsenite (modified Jacobs and Hochheiser method; hereafter referred as SA), the most widely used manual monitoring method for determination of nitrogen dioxide (NO₂) in ambient air, particularly in developing countries has been evaluated and compared with US EPA recommended equivalent method of TGS-ANSA (hereafter referred as ANSA). NO₂ concentrations generated from laboratory test atmosphere were analyzed by these two methods and were compared statistically. Laboratory evaluations showed that SA method has high sensitivity to different sampling conditions, which normally vary during actual field monitoring. Hence, correction factors for absorption efficiency were estimated for SA and ANSA methods. Absorption efficiency of NO₂ in SA method was found to be much lower (64%) as against the reported value of 82% at the method recommended sampling conditions, whereas for ANSA method, it was found 1.0 as against the reported value of 0.93. After applying derived correction factors, both the methods produced almost similar concentration values of NO₂.     

Distribution of Iron, Manganese, Zinc and Atrazine in Groundwater in Parts of Palar and Cheyyar River Basins, South India

A study was carried out in a part of Palar and Cheyyar river basin to evaluate the current status of iron, manganese, zinc and atrazine concentrations, their origin and distribution in groundwater. Groundwater samples were collected during post-monsoon (March 1998 and February 1999) and pre-monsoon (June 1999) periods from 41 sampling wells distributed throughout the study area. The groundwater samples were analyzed for trace metals using AAS and atrazine using HPLC. The concentration of the trace elements in groundwater is predominant during pre-monsoon period. Distribution pattern indicates that the concentration of these elements increases from west to northeast and towards Palar river. Lower concentrations in the central part may be due to recharge of fresh water from the lakes located here. During most of the months, as there is no flow in Palar river, the concentrations of trace elements in groundwater are high. Drinking water standards indicate that Mn and Zn cross the permissible limit recommended by EPA during the pre-monsoon period. A comparison of groundwater data with trace element chemistry of rock samples shows the abundance of trace elements both in the rock and water in the order of Fe > Mn > Zn and Fe > Zn > Mn. This indicates that iron in groundwater is derived from lithogenic origin. Further, Fe, Mn and Zn have good correlation in rock samples, while it is reverse in the case of water samples, indicating the non-lithogenic origin of Mn and Zn. Atrazine (a herbicide) was not detected in any of the groundwater samples in the study area, perhaps due to low-application rate and adsorption in the soil materials.     

Monitoring of Butter and Ghee (Clarified Butter Fat) for Pesticidal Contamination from Cotton Belt of Haryana, India

Butter (45) and ghee (55) samples were collected from rural and urban areas of cotton growing belt of Haryana and analysed for detecting the residues of organochlorine, synthetic pyrethroid and organophosphate insecticides. The estimation was carried out by using multi residue analytical technique employing GC-ECD and GC-NPD systems equipped with capillary columns. Butter samples were comparatively more contaminated (97%) than ghee (94%), showing more contamination with organochlorine insecticides from urban samples. About 11% samples of butter showed endosulfan residues above MRL value and 2% samples had residues of synthetic pyrethroids and organophosphates each above their respective MRL values. In ghee, residues of HCH & DDT both and of endosulfan exceeded the MRL values in 5 and 20% samples, respectively. Among organophosphates, only chlorpyriphos was detected with 9% samples showing its residue above MRL value. Irrespective of contamination levels, residues above the MRL values were more in ghee. More extensive study covering other agricultural regions/zones of Haryana has been suggested to know the overall scenario of contamination of milk products.