Mass loadings of triclosan and triclocarbon from four wastewater treatment plants to three rivers and landfill in Savannah, Georgia, USA.

Triclosan (TCS) and triclocarbon (TCC) are bactericides used in various consumer and personal-care products. Recent studies have revealed considerable levels of these bactericides in wastewater, aquatic wildlife, and human samples. Consequently, in this study we measured TCS and TCC in influent and effluent, sludge, and pond water/sediment samples from four wastewater treatment plants (WWTPs) and three major rivers in Savannah, Georgia (USA). Among these treatment plants, the Wilshire plant showed elevated concentrations of TCS (influent, 86,161; effluent, 5370 ng/L), whereas TCC was greater in the Georgetown plant (influent, 36,221) and the Wilshire plant effluent (3045 ng/L). Clearance of TCS and TCC were 95 and 92%, respectively, in the President Street plant, 94 and 85%, respectively, in the Wilshire plant, 99 and 80%, respectively, in the Travis Field plant, and 99 and 99%, respectively, in the Georgetown plant. Based on the mass flow estimate, 138 g/day of TCS and 214 g/day TCC are released into the Savannah River from the President Street, Travis Field, and Wilshire plants and 1.60 g/day TCS and 1.64 g/day TCC are released to the Ogeechee River from the Georgetown plant. Based on the sludge data, the loading estimate can be calculated that 32 and 0.004 g/day TCS and 53 and 0.01 g/day TCC (nonincinerated and incinerated, respectively) are deposited in landfill from the President Street plant alone, whereas 4.6, 26, and 6.8 g/day TCS and 3.8, 23, and 5.9 g/day TCC (wet sludge) were produced and dumped in landfill from the rest of the WWTPs. Incineration of wet sludge can eliminate 99.99% of TCS and TCC. Concentrations of TCS and TCC in water and sediment were greater in the Vernon River, followed by the Savannah River and the Ogeechee River.

Hexabromocyclododecane in white-sided dolphins: temporal trend and stereoisomer distribution in tissues.

Hexabromocyclododecane (HBCD) is a brominated flame retardant used primarily in expanded polystyrene foams and other styrene resins. Samples of blubber (n = 57) and liver (n = 16) from Atlantic white-sided dolphins, Lagenorhynchus acutus, that stranded on the eastern coast of United States between 1993 and 2004 were obtained from the National Marine Mammal Tissue Bank (NMMTB). Blubber samples from most of these animals (n = 47) were previously analyzed for polybrominated diphenyl ethers (PBDE), polychlorinated biphenyls (PCB), and several toxaphene congeners. The three most abundant diastereomers in the technical HBCD mixture (alpha-HBCD, beta-HBCD, and gamma-HBCD) and their enantiomers were determined using liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS). alpha-HBCD was found in all blubber and liver samples while beta-HBCD and gamma-HBCD were not detected in any samples. The alpha-HBCD concentration in blubber and liver ranged from 14 ng/g wet mass (19 ng/g lipid) to 280 ng/g wet mass (380 ng/g lipid) and 0.051 ng/g wet mass (2.9 ng/g lipid) to 3.6 ng/g wet mass (140 ng/g lipid), respectively. Concentrations of alpha-HBCD were 2 to 3 orders of magnitude lower than previously reported PBDE, PCB, and toxaphene concentrations in these same animals. There was not a significant temporal trend for these compounds in white-sided dolphin blubber. The enantiomeric fractions (EF) measured in blubber and liver were not statistically different and ranged from 0.34 to 0.53. Blubber EFs were significantly correlated with both alpha-HBCD concentrations and white-sided dolphin body length. In general, concentrations of HBCDs were lower in these white-sided dolphins than in cetaceans from Western Europe.

Synthetic musk fragrances in environmental Standard Reference Materials.

Synthetic musk fragrances have been measured in water, air, sediments, sewage sludge, and biota worldwide. As the study of the environmental fate and impacts of these compounds progresses, the need for Standard Reference Materials (SRMs) for these compounds to facilitate analytical method improvement and interlaboratory comparisons becomes increasingly important. The National Institute of Standards and Technology (NIST) issues environmental matrix SRMs with certified concentrations for a variety of persistent organic pollutants including polycyclic aromatic hydrocarbons (PAHs), chlorinated pesticides, and polychlorinated biphenyl congeners (PCBs). Until now synthetic musk fragrance concentrations have not been reported in NIST SRMs. The objective of this study was to provide reference values for several commonly detected synthetic musk fragrances in several NIST natural matrix SRMs. In this study five polycyclic musk fragrances [HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran), AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene), ADBI (4-acetyl-1,1-dimethyl-6-tert-butylindane), AHMI (6-acetyl-1,1,2,3,3,5-hexamethylindane), and ATII (5-acetyl-1,1,2,6-tetramethyl-3-isopropylindane] and two nitro musk fragrances [musk xylene (1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene) and musk ketone (4-tert-butyl-3,5-dinitro-2,6-dimethylacetophenone)] were measured in selected environmental SRMs. Gas chromatography-electron impact mass spectrometry (GC/EI-MS) was used for all analyses. HHCB was the most frequently detected synthetic musk fragrance and was detected in SRM 2585 Organic Contaminants in House Dust, SRM 2781 Domestic Sludge, SRM 1974b Organics in Mussel Tissue (Mytilus edulis), and SRM 1947 Lake Michigan Fish Tissue. It was not detected in SRM 1946 Lake Superior Fish Tissue or SRM 1945 Organics in Whale Blubber. Concentrations of HHCB in these SRMs ranged from 1.12 ng/g in SRM 1947 to 92,901 ng/g in SRM 2781. All of the polycyclic musk fragrances were detected in SRM 2781 and all of the target compounds were detected in SRM 2585.

Analysis of hexabromocyclododecane diastereomers and enantiomers by liquid chromatography/tandem mass spectrometry: chromatographic selectivity and ionization matrix effects.

Hexabromocyclododecane (HBCD) is a flame retardant that is undergoing environmental risk assessment. The liquid chromatographic retention and electrospray ionization matrix effects were investigated for HBCD methods of analysis for environmental matrices. Column selectivity towards HBCD diastereomers was evaluated for C30 and C18 stationary phases under different mobile phase conditions and column temperatures. The HBCD elution order was dependent on the shape selectivity of the stationary phase and the mobile phase composition. Greater resolution, on columns with reduced shape selectivity, of beta-HBCD and gamma-HBCD was achieved with the use of an acetonitrile/water (compared with a methanol/water) mobile phase composition. A liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method for the analysis of HBCD in biological tissues was evaluated for potential matrix effects. The influence of extracted matrix components on HBCD diastereomer and enantiomer analysis was investigated using a postextraction addition approach. Although the analysis of HBCD diastereomers was relatively unaffected by the sample matrix, the responses of the HBCD enantiomers in tissue samples were significantly influenced by matrix effects and other changes to the ionization conditions. The use of racemic 13C-labeled HBCD diastereomers as internal standards for enantiomer fraction measurements corrected for the changes in the mass spectrometer response.

Analytical methods for the determination of persistent ingredients of personal care products in environmental matrices.

Concern about the environmental fate and potential effects of synthetic organic chemicals used in soaps, lotions, toothpaste, and other personal care products continues to increase. This review describes procedures used for the analysis of five classes of these compounds-synthetic musk fragrances, antimicrobials, ultraviolet filters, insect repellents, and parabens-in water, sediment, sewage sludge, air, and aquatic biota. The primary focus is on sample extraction and preparation methods for these compounds. Instrumental methods commonly used for these compounds are also discussed.

Synthetic musk fragrances in Lake Erie and Lake Ontario sediment cores.

Two sediment cores collected from Lake Ontario and Lake Erie were sectioned, dated, and analyzed for five polycyclic musk fragrances and two nitro musk fragrances. The polycyclic musk fragrances were HHCB (Galaxolide), AHTN (Tonalide), ATII (Traseolide), ADBI (Celestolide), and AHMI (Phantolide). The nitro musk fragrances were musk ketone and musk xylene. Chemical analysis was performed by gas chromatography/mass spectrometry (GC/MS), and results from Lake Erie were confirmed using gas chromatography/triple-quadrupole mass spectrometry (GC/MS/MS). The chemical signals observed at the two sampling locations were different from each other primarily because of large differences in the sedimentation rates at the two sampling locations. HHCB was detected in the Lake Erie core whereas six compounds were detected in the Lake Ontario core. Using measured fragrance and 210Pb activity, the burden of synthetic musk fragrances estimated from these sediment cores is 1900 kg in Lake Erie and 18 000 kg in Lake Ontario. The input of these compounds to the lakes is increasing. The HHCB accumulation rates in Lake Erie for 1979-2003 and 1990-2003 correspond to doubling times of 16 +/- 4 and 8 +/- 2 years, respectively. The results reflect current U.S. production trends for the sum of all fragrance compounds.

Gas-phase concentrations of current-use pesticides in Iowa.

Local and regional atmospheric transport of current-use pesticides is an important source of these compounds to nontarget plants and ecosystems. Current-use pesticides were measured at urban, rural, and suburban sites in eastern Iowa during 2000-2002. The most detected compounds were hexachlorobenzene and trifluralin, which were found in 89% and 78% of the samples, respectively. As expected, many pesticides showed a strong seasonal trend with the most detections and highest concentrations occurring during the spring and early summer. The average detected concentrations of five heavily used herbicides were 0.52 ng/ m3 for trifluralin, 4.6 ng/m3 for acetochlor, 2.3 ng/m3 for metolachlor, 1.1 ng/m3 for alachlor, 1.7 ng/m3 for pendimethalin, and 1.2 ng/m3 for atrazine. The most frequently detected insecticides were phorate and chlorpyrifos, which were found in 20% and 19% of the samples, respectively. The average phorate and chlorpyrifos concentrations were 25 ng/m3 and 1.0 ng/m3, respectively. The maximum phorate concentration, the highest measured for all pesticides, was 91.2 ng/m3. The most frequently detected current-use fungicides were chloroneb and etridiazole, which were found in 14% and 10% of the samples, respectively.

Mass budget of perfluorooctane surfactants in Lake Ontario.

Perfluorooctane surfactants have been reported in biota, water, and air samples worldwide. Despite these reports, the main environmental sources of these compounds remain undefined. To address this gap in knowledge, an annual lake-wide mass budget of eight perfluorooctane surfactants was developed for Lake Ontario. To determine the atmospheric contribution to the mass budget, over-the-lake gas-phase air concentrations for N-EtFOSE and N-EtFOSA and particulate-phase air concentrations for PFOS in any air sample are reported for the first time, with mean concentrations when present of 0.5+/-0.32 (N-EtFOSE gas-phase), 1.1+/-0.9 (N-EtFOSA gas-phase), and 6.4+/-3.3 (PFOS particulate-phase) pg/m3. The mass budget finds inflow from Lake Erie (14 361+/-4489 kg sigma perfluorooctane surfactants) and wastewater discharge (1762+/-2697 kg sigma perfluorooctane surfactants) to be the major sources, while outflow through the St. Lawrence River is the dominant loss mechanism (22,727+/-7060 kg/year sigma perfluorooctane surfactants). Using the mass budget data, the steady state and measured mean concentrations in the lake water are the same at the 95% confidence level.

Synthetic musk fragrances in Lake Michigan.

Synthetic musk fragrances are added to a wide variety of personal care and household products and are present in treated wastewater effluent. Here we report for the first time ambient air and water measurements of six polycyclic musks (AHTN, HHCB, ATII, ADBI, AHMI, and DPMI) and two nitro musks (musk xylene and musk ketone) in North America. The compounds were measured in the air and water of Lake Michigan and in the air of urban Milwaukee, WI. All of the compounds except DPMI were detected. HHCB and AHTN were found in the highest concentrations in all samples. Airborne concentrations of HHCB and AHTN average 4.6 and 2.9 ng/m3, respectively, in Milwaukee and 1.1 and 0.49 ng/m3 over the lake. The average water concentration of HHCB and AHTN in Lake Michigan was 4.7 and 1.0 ng/L, respectively. A lake-wide annual mass budget shows that wastewater treatment plant discharge is the major source (3470 kg/yr) of the synthetic musks while atmospheric deposition contributes less than 1%. Volatilization and outflow through the Straits of Mackinac are major loss mechanisms (2085 and 516 kg/yr for volatilization and outflow, respectively). Concentrations of HHCB are about one-half the predicted steady-state water concentrations in Lake Michigan.