Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.     

Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

MULTI INCREMENT® TCE vadose‐zone investigation

MULTI INCREMENT® and discrete sampling strategies were used to estimate the average concentration and the three‐dimensional distribution of TCE in a 3,300‐m³ zone composed of two decision units (e.g., area of concern, population, exposure unit). Authors of this article and a private contractor (Stanley Consultants Inc.), respectively, implemented these two sampling strategies independently. Compared to discrete sampling, the MULTI INCREMENT sampling strategy identified more locations where percent‐level concentrations of TCE have migrated, is more economical, and provided greater data quality. © 2008 Wiley Periodicals, Inc.     

Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter(-1), with three different filter loadings denoted "Low", "Medium" and "High". Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter(-1). Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study.     

Receptor model-based source apportionment of particulate pollution in Hyderabad, India

Air quality in Hyderabad, India, often exceeds the national ambient air quality standards, especially for particulate matter (PM), which, in 2010, averaged 82.2?±?24.6, 96.2?±?12.1, and 64.3?±?21.2 μg/m³ of PM₁₀, at commercial, industrial, and residential monitoring stations, respectively, exceeding the national ambient standard of 60 μg/m³. In 2005, following an ordinance passed by the Supreme Court of India, a source apportionment study was conducted to quantify source contributions to PM pollution in Hyderabad, using the chemical mass balance (version 8.2) receptor model for 180 ambient samples collected at three stations for PM₁₀ and PM_2.5 size fractions for three seasons. The receptor modeling results indicated that the PM₁₀ pollution is dominated by the direct vehicular exhaust and road dust (more than 60 %). PM_2.5 with higher propensity to enter the human respiratory tracks, has mixed sources of vehicle exhaust, industrial coal combustion, garbage burning, and secondary PM. In order to improve the air quality in the city, these findings demonstrate the need to control emissions from all known sources and particularly focus on the low-hanging fruits like road dust and waste burning, while the technological and institutional advancements in the transport and industrial sectors are bound to enhance efficiencies. Andhra Pradesh Pollution Control Board utilized these results to prepare an air pollution control action plan for the city.     

The importance of small urbanized watersheds to pollutant loading in a large oligotrophic subalpine lake of the western USA

Urban land use has been implicated as a major contributor of nonpoint source pollution in aquatic systems. Through increased nonpoint delivery of pollutants, including constituents found in stormwater, Lake Tahoe is undergoing a marked decline in its transparency, primarily due to increasing production of algae from enhanced nutrient loading and delivery of fine particles to the lake from the watershed. In response to these findings, a regional restoration effort is underway to improve basin watersheds and the water quality in Lake Tahoe. In this study, stormwater autosamplers were used to collect flow-weighted composite samples that characterized event mean concentrations for event and nonevent conditions within a small, urbanized watershed in the Tahoe basin. An event-specified constant-concentration water quality model was then applied to the event mean concentration and continuous streamflow data to estimate pollutant loads for nitrate, nitrite, ammonia, orthophosphate, and suspended sediment. These data were compared with previously reported load estimates from 10 primary monitored streams in larger watersheds of the Tahoe basin. Results from a linear regression analysis demonstrate strong and significant relationships between watershed impervious area and pollutant loadings from Lake Tahoe watersheds. These small, urbanized watersheds and intervening zones, which only comprise 10 % of the total Lake Tahoe drainage area, include a significant portion of the total Lake Tahoe impervious area. The findings of this study suggest that small, urbanized watersheds and intervening zones are disproportionately important contributors of nonpoint source pollution, including nutrients and suspended particles.     

Integration of long-term fish kill data with ambient water quality monitoring data and application to water quality management

Almost half (354) of all fish kills (805) in South Carolina, USA, between 1978 and 1988 occurred in the coastal zone. These kills were analyzed for causative, spatial, and temporal associations as a distinct data set and as one integrated with ambient water quality monitoring data. Estuarine kills as a result of natural causes accounted for 42.8% followed by man-induced (35.1%) and undetermined causes (22.1%). Although general pesticide usage was responsible for 53.9% of man-induced kills, weed control activities around resorts and municipal areas accounted for slightly more kills (20.9%) than did agricultural (19.8%) or vector control (13.2%) uses. A dramatic decline in agricultural-related kills has been observed since 1986 as the integrated pest management approach was adopted by many farmers. When taken with the few kills (12.0%) resulting from wastewaters, this suggests that these two land-use activities have been successfully managed via existing programs (IPM and NPDES, respectively) to minimize their contributions to estuarine fish kills. Ambient trend monitoring data demonstrated no coastal-wide dispersion of pesticide pollution. These data confirmed the nature of fish kills to be site-specific, near-field events most closely associated with the contiguous land-use practices and intensities. Typically, fish kill data are considered as event-specific data limited to the bounds of that event only. Our analysis has shown, however, that a long-term data set, when integrated with ambient water quality data, can assist in regulatory and resource management decisions for both short- and long-term planning and protection applications.     

INACTIVATION OF GIARDIA MURIS CYSTS BY CHLORAMINES1

ABSTRACT: In a study to measure the efficacy of chioramines at inactivating Giardia cysts, the ability of cysts to excyst was measured after exposure to different concentrations of chloramines, for different times, and at different temperatures and pH. The chloramines were generated by mixing ammonium sulfate and sodium hypochlorate in water to approximate a 7:1 chlorine:ammonia ratio by weight. Times of 40, 80, 180, and 270 minutes; temperatures of 3, 10, and 18°C; target chioramine concentrations of 0.4, 1.4, 2.0, and 2.6 mg/L; and pH of 7.0 and 8.5 were the actual values tested. The combinations of these variables that were able to inactivate >99.8 percent of the cysts were a minimum chloramine concentration of 2.26 mg/L applied for 270 minutes at a water temperature of 10°C; and at 18°C, averaged minimum chloramine concentrations of 2.14 and 1.55 mg/L applied for 180 and 270 minutes, respectively. The minimum CT values corresponding to these combinations capable of >99.8 percent cyst inactivation, are 610 at 10°C and 385 at 18°C. Temperature was noted to exert a major effect on the ability of chloramines to inactivate cysts. Modifications of the methods used to generate chloramines may have an effect on the capacity of this disinfectant to inactivate cysts.     

EFFECTS OF PLACER MINING DISCHARGE ON HEALTH AND FOOD OF ARCTIC GRAYLING1

ABSTRACT: During the summers of 1982, 1983, and 1985, we assessed the effects of placer mining sedimentation on Arctic grayling, Thymallus arcticus, in the headwaters of Birch Creek, northeast of Fairbanks, Alaska. We compared differences between two streams (one that was undisturbed and one with mining activity upstream) near the confluence. Studies of caged fish demonstrated that, if grayling could not escape from streams carrying mining sediments, they would either die at high rates (sac fry) or suffer gill damage, starvation, and slowed maturation (age-O fingerlings and age-2 juveniles). Indirect effects of sedimentation, through loss of summer habitat for feeding and reproduction, may more severely affect grayling populations than the direct effects of sedimentation on the health and survival of individual fish.