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.

Distribution of persistent organohalogen compounds in pine needles from selected locations in Kentucky and Georgia, USA.

Epicuticular wax of pine needles accumulates organic pollutants from the atmosphere, and the pine needle samples have been used for monitoring both local and regional distributions of semivolatile organic air pollutants. One-year-old pine needles collected from residential and industrial locations in western Kentucky and the vicinity of Linden Chemicals and Plastics, a Superfund Site at Brunswick, Georgia, were analyzed for polychlorinated biphenyls (PCBs), major chlorinated pesticides, and polychlorinated naphthalenes (PCNs). Total PCB concentrations in pine needles from Kentucky ranged from 5.2 to 12 ng/g dry weight (dw). These sites were comparatively less polluted than those from the Superfund Site, which had total PCB concentrations in pine needles in the range of 15-34 ng/g dw. Total chlorinated pesticides concentrations in pine needles ranged from 3.5 to 10 ng/g dw from Kentucky. A similar range of concentrations of chlorinated pesticides (7.3-12 ng/g dw) was also found in pine needle samples from the Superfund site. Total PCN concentrations in pine needles ranged from 76 to 150 pg/g dw in Kentucky. At the Superfund Site, total PCN concentrations ranged from 610 pg/g dw to 38,000 pg/g dw. When the toxic equivalencies (TEQs) of PCBs in pine needles were compared, Kentucky was relatively lower (0.03-0.11 pg/g dry wt) than the TEQs at the Superfund Site (0.24-0.48 pg/g dry wt). The TEQs of PCNs from Kentucky (0.004-0.067 pg/g dw) were much lower than the TEQs from locations near the Superfund Site (0.30-19 pg/g dry wt). The results revealed that pine needles are excellent, passive, nondestructive bioindicators for monitoring and evaluating PCBs, chlorinated pesticides, and PCNs.

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in sediment and mussel samples from Kentucky Lake, USA.

Sediment and mussel tissues from the Kentucky Dam Tailwater (KDTW) and Ledbetter Embayment (LE) of Kentucky Lake, Kentucky, USA, were analyzed to examine the presence of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and non-, mono-, and di-ortho-chlorine-substituted polychlorinated biphenyls. Concentrations of target compounds varied with locations and sample matrices. In general, KDTW sediment samples contained slightly higher amounts of PCDD/DFs (average: 1100, range: 120-2400) than the LE sediments (average: 920, range: 580-1300) on a pg/g dry wt (dw) basis. Dioxin-like PCBs in KDTW were (average: 550, range: 70-2,000) higher than in LE (average: 320, range: 44-1000) on a ng/g dw basis. In contrast, mussel tissues had greater concentrations of PCDD/DFs in LE (average: 6500, range: 2200-13,000) than in KDTW (average: 3500, range: 2500-4800). Dioxin-like PCBs were slightly higher in KDTW (average: 76, range: 18-100) than in LE (average: 49, range: 24-96) on a ng/g fat wt basis. Biota sediment accumulation factors (BSAFs) were calculated using tissue concentrations and sediment concentrations based on dry weight. PCDD/DFs BSAF was in the range of 0.21-25 in LE and 0.093-13 in KDTW. 1,2,3,7,8,9-HxCDF in LE and 2,3,7,8-TCDF in KDTW had a greater BSAF, while BSAF for dioxin-like PCBs ranged from 0.84 to 13 in LE and from 2.3 to 12 in KDTW in which PCB-169 had the greatest BSAF in LE and PCB-167 in KDTW. Toxic equivalency (TEQ) was greatest in mussel from LE (mean: 193 pgTEQ/g fat wt) followed by mussel from KDTW (32 pgTEQ/g fat wt), sediment in KDTW (13 pgTEQ/g dry wt), and sediment in LE (7.6 pgTEQ/g dry wt). In general, PCDD/DF had a greater contribution to toxicity in mussels, while dioxin-like PCBs had a greater contribution to toxicity in sediment at both locations.

Elemental status in sediment and American oyster collected from Savannah marsh/estuarine ecosystem: a preliminary assessment.

Sediment and American oyster (Crassostrea virginica) collected from nine selected marsh/estuarine ecosystems in Savannah, Georgia were analyzed for elements such as Al, As, B, Cd, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Si, and Zn. Sediments were extracted by ammonium acetate (NH(4)OAc), Mehlich-3 (M-3), and water procedures, whereas an acid digestion procedure was adopted for oyster tissue. Concentrations of elements were higher in M-3 extractions followed by NH(4)OAc and water extraction procedures. Calcium and Mg was greater in sediments by any of the extractions, whereas other elements differed depending upon the extraction procedures. There were no significant spatial variations (p < 0.05) of any of elements analyzed except Mn, in NH(4)OAc/water extraction procedure and Fe and Al by water extraction procedure. Contamination of Al, B, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Si, and Zn in oyster tissue ranged from 399 to 1460, 231 to 254, <1.5 to 2.9, <1.5 to 8.0, 67 to 121, 232 to 1357, 17 to 54, <0.5 to 0.64, <1.5 to 2.5, <1.5 to 4.0, 241 to 381, and 978 to 2428 microg/g dry weight (dw), respectively. Greatly elevated concentrations of elements such as P, Ca, Mg, K, and S were noticed in oyster tissue. The concentration range of Hg and As in sediment was 1.2-1.9 and 11-55 microg/g dw, respectively. The concentration range of Hg and As in oyster tissue was 130-908 and 200-912 ng/g dw, respectively. With the exception of As and Hg, other elements are several orders of magnitude greater in oyster tissue. There is no significant (p < 0.05) contamination variation in target analyses between the nine selected sites. Concentrations of heavy metals in sediment and oyster were either comparable or lower than those of other countries. Greater biota-sediment accumulation factor was noticed for P and Zn. Concentrations of Hg and P in oyster tissue were higher than the threshold limit for human consumption. Overall, the baseline data can be used for regular ecological monitoring, considering the domestic and industrial growth around this important marsh/estuarine ecosystem.

Role of temperature and hydrochloric acid on the formation of chlorinated hydrocarbons and polycyclic aromatic hydrocarbons during combustion of paraffin powder, polymers, and newspaper.

Formation of chlorinated hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) were determined using a laboratory-scale incinerator when combusting materials at different temperatures, different concentrations of hydrochloric acid (HCl), and when combusting various types of polymers/newspaper. Polychlorobenzenes (PCBz), polychlorophenols (PCPhs), polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and their toxic equivalency (TEQ) and PAHs were highlighted and reported. Our results imply maximum formation of chlorinated hydrocarbons at 400 degrees C in the following order; PCBz>or=PCPhs>>PCDFs>PCDDs>TEQ on a parts-per-billion level. Similarly, a maximum concentration of chlorinated hydrocarbons was noticed with an HCl concentration at 1000 ppm with the presence of paraffin powder in the following order; PAHs>PCBz>or=PCPhs>>PCDFs>PCDDs>TEQ an a parts-per-billion level. PAHs were not measured at different temperatures. Elevated PAHs were noticed with different HCl concentrations and paraffin powder combustion (range: 27-32 microg/g). While, different polymers and newspaper combusted, nylon and acrylonitrile butadiene styrene (ABS) produced the maximum hydrogen cyanide (HCN) concentration, concentrations of PCDD/FS, dioxin-like polychlorinated biphenyls (DL-PCBs), and TEQ were in a decreasing order: polyvinylchloride (PVC)

Chemical characterization of polychlorinated biphenyls, -dibenzo-p-dioxins, and -dibenzofurans in technical Kanechlor PCB formulations in Japan.

Technical polychlorinated biphenyl (PCB) formulations-Kanechlor KC-200, KC-300, KC-400, KC-500, KC-600 and KC-1000-produced in Japan were analyzed for the chemical characterization of PCBs, -dibenzo-p-dioxins (PCDDs), and -dibenzofurans (PCDFs) using high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS) by isotope dilution technique. The homologue/congener profiles of Kanechlor formulations resembled those of Clophen, Aroclor, and Delor, respectively, from Germany, the United States, and Czechoslovakia. Twenty-seven major PCB congeners contributed 50% (in KC-200) to 69-71% (in KC-600, 1000, and 500) to total PCBs. Average total PCB concentrations were 510,000, 800,000, 830,000, 840,000, 870,000, and 880,000 mug/g in KC-1000 (51%), KC-200 (80%), KC-500 (83%), KC-400 (84%), KC-300 (87%), and KC-600 (88%), respectively. Kanechlors also contained PCDDs and PCDFs (4.3 to 0.35 microg/g) as impurities which were approximately 1/10,000 to the PCB concentrations. Congener characterization and concentrations of PCBs and PCDFs were considerably varied in between Kanechlor formulations. The potential for the emissions of PCDDs and PCDFs from Kanechlor was estimated to be 1.94 kg and 464.4 kg, respectively. The average WHO-toxic equivalent (TEQ) was 16 (KC-500) >12 (KC-400) >10 (KC-1000) >4.1 (KC-600) >3.5 (KC-300) >1.9 (KC-200) on microgTEQ/g. Non- and mono-ortho PCBs were the major contributors to the total TEQ in Kanechlor formulations, whereas the PCDD/DF contribution was <2.0%. The environmental input of TEQs from Kanechlors can be estimated to be between 112 and 941 kg.

Analysis of UNEP priority POPs using HRGC-HRMS and their contamination profiles in livers and eggs of great cormorants (Phalacrocorax carbo) from Japan.

The present investigation demonstrates establishment of United Nations Environment Programme (UNEP) priority Persistent Organic Pollutants (POPs) using high-resolution gas chromatography-high-resolution mass spectrometry. Particularly, POPs analytical methods were established using native and (13)C-labeled internal standards of HCHs, HCB, cyclodienes, chlordanes, DDTs, mirex, dioxin-like PCBs, PCDDs, and PCDFs by isotope dilution technique. The relative response factor for 6-point calibration curve native standards (18 replicate analysis) were in the ranges of 0.93-1.43 with relative standard deviation ranges from 1.68 to 4.96%. Instrument detection limit and instrument quantification limit was established for various POPs at femtograms. Concentrations of UNEP-POPs were measured in liver (n = 10) and egg (n = 10) of great cormorants and their major diet, gizzard shad (n = 2), collected in and around Tokyo, Japan. DDTs (ranges in liver and egg, respectively) were predominant accumulants (9800-310,000 and 9600-73,000) followed by dioxin-like PCBs (4500-69,000 and 7900-150,000), chlordanes (2600-16,000 and 700-4,800), cyclodienes (650-4600 and <1-1000), HCB (680-2800 and 180-590), HCHs (230-1800 and 120-490), PCDD/DFs (3.2-27 and 1.7-5.7) on nanogram per gram lipid basis. Concentrations (ranges) of POPs in gizzard shad were in the following order: DDTs (3900-16,000), chlordanes (3400-14,000), cyclodienes (340-1300), HCB (110-480), and HCHs (140-360) on nanogram per gram lipid basis.

Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries.

Perfluorooctanesulfonyl fluoride based compounds have been used in a wide variety of consumer products, such as carpets, upholstery, and textiles. These compounds degrade to perfluorooctanesulfonate (PFOS), a persistent metabolite that accumulates in tissues of humans and wildlife. Previous studies have reported the occurrence of PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) in human sera collected from the United States. In this study, concentrations of PFOS, PFHxS, PFOA, and PFOSA were measured in 473 human blood/serum/plasma samples collected from the United States, Colombia, Brazil, Belgium, Italy, Poland, India, Malaysia, and Korea. Among the four perfluorochemicals measured, PFOS was the predominant compound found in blood. Concentrations of PFOS were the highest in the samples collected from the United States and Poland (>30 ng/mL); moderate in Korea, Belgium, Malaysia, Brazil, Italy, and Colombia (3 to 29 ng/mL); and lowest in India (<3 ng/mL). PFOA was the next most abundant perfluorochemical in blood samples, although the frequency of occurrence of this compound was relatively low. No age- or gender-related differences in the concentrations of PFOS and PFOA were found in serum samples. The degree of association between the concentrations of four perfluorochemicals varied, depending on the origin of the samples. These results suggested the existence of sources with varying levels and compositions of perfluorochemicals, and differences in exposure patterns to these chemicals, in various countries. In addition to the four target fluorochemicals measured, qualitative analysis of selected blood samples showed the presence of other perfluorochemicals such as perfluorodecanesulfonate (PFDS), perfluoroheptanoic acid (PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA), and perfluoroundecanoic acid (PFUnDA) in serum samples, at concentrations approximately 5- to 10-fold lower than the concentration of PFOS. Further studies should focus on identifying sources and pathways of human exposure to perfluorochemicals.

Formation of polychlorinated naphthalenes, dibenzo-p-dioxins, dibenzofurans, biphenyls, and organochlorine pesticides in thermal processes and their occurrence in ambient air.

Mono- through octachlorinated naphthalenes (PCNs) were measured in start-up, steady operation, and shutdown of machinery operation flue gas and fly ash generated during different stages of MSWI and other incineration thermal processes. Besides, electroprecipitator fly ash (EP-ash) was dechlorinated using the Hagenmeier process and analyzed for congener profiles. In addition to PCNs, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and major organochlorine pesticides were determined in ambient air samples from three different sites of western Japan in the summer and winter of 1992. The PCNs from flue gas contained 15,000, 4300, and 13,000 ng/m3 during start-up, steady operation, and shutdown conditions, respectively. Whereas fly ash contained 470, 370, and 1400 ng/g PCNs under start-up, steady operation, and shutdown condition, respectively. The dechlorination process reduced PCN concentrations considerably. Concentrations of PCNs and PCDD/PCDFs in air samples collected in winter were slightly higher than in summer. PCBs, organochlorine pesticides such as chlordanes, DDTs, and HCHs were higher in summer air samples. WHO toxic equivalency (WHO-TEQ) concentrations in air samples were 0.3-0.9 pg/m3 for PCDD/DFs and 0.029-0.31 pg/m3 for dioxin-like PCBs.

Polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls in polar bear, penguin and south polar skua.

Concentrations of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (DFs) and non- and mono-ortho-substituted polychlorinated biphenyls (dioxin-like PCBs) were measured in livers of polar bears from the Alaskan Arctic and in eggs of Adelie penguin and south polar skua and weddell seal liver, fish and krill from Antarctica. This is one of the first reports to document the concentrations of PCDDs/DFs in polar bear livers from Alaska, and in penguin and skua eggs from Antarctica. Concentrations of total PCDD/DFs in livers of polar bears ranged from 8 to 66 (mean: 26) pg/g, on a lipid weight basis. Concentrations of total PCDD/DFs in Antarctic samples were in the increasing order on a lipid weight basis; weddell seal liver (8.9 pg/g) < fish (11-17 pg/g) < krill (27 pg/g) > penguin eggs (30 ng/g) > seal liver (57 ng/g) > fishes (6.2 ng/g) > krill (0.9 ng/g). Concentrations of 2378-tetrachlorodibenzo-p-dioxin equivalents (TEQs) calculated based on the WHO TEFs were higher in the eggs of polar skua (mean: 344: range: 220-650 pg/g, lipid wt.) from Antarctica than in polar bear livers from Alaska (mean: 120; range: 69-192 pg/g). In general, concentrations of PCDFs were greater than those of PCDDs in polar organisms. 23478-PeCDF is one of the dominant congener found in several samples. Concentrations of TEQs in polar bear livers and skua eggs were close to those that may cause adverse health effects. Dioxin-like PCBs, particularly, non-ortho coplanar PCBs were the major contributors to TEQ concentrations in penguin and skua eggs whereas mono-ortho PCBs accounted for a major portion of TEQs in polar bear livers.

Distribution and elimination of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, and p,p'-DDE in tissues of bald eagles from the Upper Peninsula of Michigan.

Liver, muscle, fat, kidney, and gall bladder of eight bald eagles (Haliaeetus leucocephalus) found dead in the Upper Peninsula of Michigan during 2000 were analyzed for the presence of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (including coplanar PCBs), p,p'-DDE, and hexachlorobenzene (HCB). Necropsy results showed that the birds suffered from peritonitis, bacterial infection, or trauma. Concentrations of PCDD/DFs in livers ranged from 23 to 4500 pg/g on a wet weight basis (wet wt), whereas the least concentrations were found in blood plasma of bald eagle nestlings (2.3-49 pg/g, wet wt). A maximum total PCB concentration of 280,000 ng/g, wet wt, was found in the liver of a dead bald eagle affected by peritonitis. The greatest concentrations of p,p'-DDE and HCB in eagle livers were 17,000 and 120 ng/g, wet wt, respectively. Eagles with elevated 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) or total PCB concentrations tended to have great TCDD/TCDF or PCB126/PCB77 ratios, hypothesized to be due to induction of cytochrome P450 enzymes and subsequent metabolism of TCDF and PCB77. Concentrations of TCDD toxic equivalents (TEQs) in the tissues of bald eagles exceeded the thresholds for toxicity in a few avian species. Non-ortho coplanar PCBs accounted for 68-88% of the total TEQs in bald eagle tissues. PCDDs and PCDFs collectively accounted for, on average, 17% of the total TEQs. On the basis of the analysis of a single gall bladder with bile, biliary excretion rates of PCDDs, PCDFs, and PCBs were estimated as 0.015-0.02% per day.