Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Assessment of dietary exposure to PCDD/F and dioxin-like PCB in infant formulae available on the EU market

In infant period, human milk and infant formulae are the major sources of exposure to dioxins (polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (PCB). Since in many parts of Europe the mothers are increasingly reluctant to breastfeed their babies, the main objective of the present study is to assess the level of exposure of non-breast-fed infants during their early development. Consequently, the concentration levels of PCDD/F and dioxin-like PCB were determined in industrial infant formulae including "starting" (aged 0-4months) and "follow-on" (after 4months) products of milk formula, soy formula and hypoallergenic infant formula, available on the EU market. Furthermore, dietary exposure to dioxin of exclusively formula-fed infants was assessed at each month from 0 to 9months. The results suggest that dietary exposure to dioxins via formulae is higher when consuming "starting" than "follow-on" infant formulae on a body-weight basis. Estimated dietary exposure after 4months of age was always below the lowest range of the Tolerable Daily Intake (TDI) of 1pg WHO-TEQkg(-1)bwd(-1) and Provisional Tolerable Monthly Intake (PTMI) of 70pg WHO-TEQkg(-1)bwmonth(-1). The highest estimated cumulative dietary exposure to PCDD/F and dioxin-like PCB was obtained considering infants of 0-1months fed with the "starting" hypoallergenic infant formula (2.8pg WHO-TEQkg(-1)bwd(-1) and 84pg WHO-TQkg(-1)bwmonth(-1)). However, these elevated levels are much lower than those observed in some studies in breast-fed infants. The study can be used for further risk assessments in regard to infant exposure.     

Aerosol speciation and mass prediction from toluene oxidation under high NOx conditions

A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO_x conditions (VOC/NO_x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m^?3 (range of 5–145 μg m^?3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73–88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO_x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO_x conditions. Further research into the yields and speciation leading to this reaction product is recommended.     

Acute toxicity of aromatic and non-aromatic fractions of naphthenic acids extracted from oil sands process-affected water to larval zebrafish

The toxicity of oil sands process-affected water (OSPW) has regularly been attributed to naphthenic acids, which exist in complex mixtures. If on remediation treatment (e.g., ozonation) or on entering the environment, the mixtures of these acids all behave in the same way, then they can be studied as a whole. If, however, some acids are resistant to change, whilst others are not, or are less resistant, it is important to establish which sub-classes of acids are the most toxic.     

Change in Pulmonary Function in Children Associated with Air Pollution Episodes

Pulmonary function of approximately 200 school children in Steubenville, OH was measured before and immediately following air pollution alerts in the fall of 1978 and 1979. TSP concentrations exceeded the National Primary Ambient Air Quality 24 h standards in 1978. SO₂ exceeded the standard in 1979. The children were then reexamined in three weekly visits following each alert. Estimated mean Forced Vital Capacity (FVC) was approximately 2% lower following each alert, although the lowest means were observed one to two weeks after the episodes. Forced Expired Volume in 0.75 sec (FEV_0.75) did not change during the 1978 study, but was 4% lower immediately following the 1979 alert. The children were measured again in five weekly examinations in the spring and fall of 1980. Air pollution levels did not exceed the standards on either occasion. In the spring of 1980, estimated mean FVC and FEV_0.75 showed a decline similar to that observed following the alerts in 1978 and 1979. In the fall of 1980, there were no significant differences in the estimated mean FVC or FEV_0.75 between the examinations. A total of 335 children were tested in the four studies, including 194 who participated in more than one study. The evidence for each child from all the studies was combined in a regression analysis of pulmonary function on TSP and SO₂ average concentrations in the previous 24 h. The distribution of the individual regression coefficients was centered significantly below zero, implying a decrease in pulmonary function with increasing TSP and SO₂ concentrations. The magnitude of the median change was less than 1% of the mean FVC and FEV_0.75 over the range of TSP and SO₂ concentrations observed.     

Influence of organic waste type and soil structure on the bacterial filtration rates in unsaturated intact soil columns

Organic wastes are considered to be a source for the potentially pathogenic microorganisms found in surface and sub-surface water resources. Following their release from the organic waste matrix, bacteria often infiltrate into soil and may be transported to significant depths contaminating aquifers. We investigated the influence of soil texture and structure and most importantly the organic waste properties on the transport and filtration coefficients of Escherichia coli and total bacteria in undisturbed soil columns. Intact soil columns (diameter 16 cm and height 25 cm) were collected from two soils: sandy clay loam (SCL) and loamy sand (LS) in Hamadan, western Iran. The cores were amended with cow manure, poultry manure and sewage sludge at a rate of 10 Mg ha(-1) (dry basis). The amended soil cores were leached at a steady-state flux of 4.8 cm h(-1) (i.e. 0.12 of saturated hydraulic conductivity of the SCL) to a total volume of up to 4 times the pore volume of the columns. The influent (C(0)) and effluent (C) were sampled at similar time intervals during the experiments and bacterial concentrations were measured by the plate count method. Cumulative numbers of the leached bacteria, filtration coefficient (lambda(f)), and relative adsorption index (S(R)) were calculated. The preferential pathways and stable structure of the SCL facilitated the rapid transport and early appearance of the bacteria in the effluent. The LS filtered more bacteria when compared with the SCL. The effluent contamination of poultry manure-treated columns was greater than the cow manure- and sewage sludge-treated ones. The difference between cow manure and sewage sludge was negligible. The lambda(f) and S(R) values for E. coli and total bacteria were greater in the LS than in the SCL. This indicates a predominant role for the physical pore-obstruction filtration mechanisms as present in the poorly structured LS vs. the retention at adsorptive sites (chemical filtration) more likely in the better structured SCL. While the results confirmed the significant role of soil structure and preferential (macroporous) pathways, manure type was proven to have a major role in determining the maximum penetration risk of bacteria by governing filtration of bacteria. Thus while the numbers of bacteria in waste may be of significance for shallow aquifers, the type of waste may determine the risk for microbial contamination of deep aquifers.     

Lateral movement of soil fumigants 1,3-dichloropropene and chloropicrin from treated agricultural fields

The soil fumigants 1,3-dichloropropene (1,3-D) and chloropicrin (CP) are often used for controlling soil-borne plant pathogens and parasitic nematodes before reestablishing new vineyards and orchards. To evaluate crop safety and environmental risks with the replant fumigation, four field experiments were performed over 2 yr to examine 1,3-D and CP lateral movement away from the treated fields. Shank injection with or without a virtually impermeable film (V1F) was used in two vineyard fumigation experiments, and spot drip application without tarp cover was used in two orchard experiments. Results showed that 1,3-D and CP gases moved laterally to 6 m from the treated fields when the fumigants were applied by shank injection. The maximum 1,3-D or CP soil gas concentration at 6 m was approximately 10 ng cm(-3) when the fumigated plot was not cover with a tarp. With VIF, the measured maximum concentration increased to approximately 100 ng cm(-3). In the spot drip application, maximum 1,3-D and CP gas concentrations reached approximately 100 ng cm(-3) but at 1.5 m radial distance from the point of fumigant injection.     

Boosted Regression Tree Models to Explain Watershed Nutrient Concentrations and Biological Condition

Boosted regression tree (BRT) models were developed to quantify the nonlinear relationships between landscape variables and nutrient concentrations in a mesoscale mixed land cover watershed during base‐flow conditions. Factors that affect instream biological components, based on the Index of Biotic Integrity (IBI), were also analyzed. Seasonal BRT models at two spatial scales (watershed and riparian buffered area [RBA]) for nitrite‐nitrate (NO₂‐NO₃), total Kjeldahl nitrogen, and total phosphorus (TP) and annual models for the IBI score were developed. Two primary factors — location within the watershed (i.e., geographic position, stream order, and distance to a downstream confluence) and percentage of urban land cover (both scales) — emerged as important predictor variables. Latitude and longitude interacted with other factors to explain the variability in summer NO₂‐NO₃ concentrations and IBI scores. BRT results also suggested that location might be associated with indicators of sources (e.g., land cover), runoff potential (e.g., soil and topographic factors), and processes not easily represented by spatial data indicators. Runoff indicators (e.g., Hydrological Soil Group D and Topographic Wetness Indices) explained a substantial portion of the variability in nutrient concentrations as did point sources for TP in the summer months. The results from our BRT approach can help prioritize areas for nutrient management in mixed‐use and heavily impacted watersheds.     

A Water Allocation Decision‐Support Model and Tool for Predictions in Ungauged Basins in Northeast British Columbia,Canada

Pressures on water resources due to changing climate, increasing demands, and enhanced recognition of environmental flow needs result in the need for hydrology information to support informed water allocation decisions. However, the absence of hydrometric measurements and limited access to hydrology information in many areas impairs water allocation decision‐making. This paper describes a water balance‐based modeling approach and an innovative web‐based decision‐support hydrology tool developed to address this need. Using high‐resolution climate, vegetation, and watershed data, a simple gridded water balance model, adjusted to account for locational variability, was developed and calibrated against gauged watersheds, to model mean annual runoff. Mean monthly runoff was modeled empirically, using multivariate regression. The modeled annual runoff results are within 20% of the observed mean annual discharge for 78% of the calibration watersheds, with a mean absolute error of 16%. Modeled monthly runoff corresponds well to observed monthly runoff, with a median Nash–Sutcliffe statistic of 0.92 and a median Spearman rank correlation statistic of 0.98. Monthly and annual flow estimates produced from the model are incorporated into a map‐ and watershed‐based decision‐support system referred to as the Northeast Water Tool, to provide critical information to decision makers and others on natural water supply, existing allocations, and the needs of the environment.