Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.     

Polycyclic musks in green-lipped mussels (Perna viridis) from Hong Kong

Six polycyclic musk compounds [Cashmeran (DPMI), Celestolide (ADBI), Phantolide (AHMI), Traseolide (ATII), Tonalide (AHTN), and Galaxolide (HHCB)] were analysed in marine green-lipped mussels (Perna viridis) from Hong Kong. ADBI, HHCB and AHTN were detected in almost all samples, while AHMI, ATII and DPMI were not detected. Concentrations of ADBI, HHCB and AHTN in mussels ranged from below detection limit-0.0743 (mean: 0.0246), 0.247-6.08 (mean: 1.15) and 0.0591-0.738 (mean: 0.190)mg/kg lipid weight, respectively. Mussels from two sampling sites in central Victoria Harbour contained the highest total polycyclic musk levels, suggesting that these waters are heavily influenced by domestic sewage. Concentrations of HHCB and AHTN detected in the mussel samples were the second highest and the highest levels, respectively, compared to global concentrations. A preliminary risk assessment indicated that HHCB and AHTN in mussels pose little or no threat to the health of shellfish consumers. Nevertheless, more comprehensive studies are required to further assess the ecological and human health risks associated with polycyclic musks.     

Polycyclic musks in green-lipped mussels (Perna viridis) from Hong Kong

Six polycyclic musk compounds [Cashmeran (DPMI), Celestolide (ADBI), Phantolide (AHMI), Traseolide (ATII), Tonalide (AHTN), and Galaxolide (HHCB)] were analysed in marine green-lipped mussels (Perna viridis) from Hong Kong. ADBI, HHCB and AHTN were detected in almost all samples, while AHMI, ATII and DPMI were not detected. Concentrations of ADBI, HHCB and AHTN in mussels ranged from below detection limit–0.0743 (mean: 0.0246), 0.247–6.08 (mean: 1.15) and 0.0591–0.738 (mean: 0.190) mg/kg lipid weight, respectively. Mussels from two sampling sites in central Victoria Harbour contained the highest total polycyclic musk levels, suggesting that these waters are heavily influenced by domestic sewage. Concentrations of HHCB and AHTN detected in the mussel samples were the second highest and the highest levels, respectively, compared to global concentrations. A preliminary risk assessment indicated that HHCB and AHTN in mussels pose little or no threat to the health of shellfish consumers. Nevertheless, more comprehensive studies are required to further assess the ecological and human health risks associated with polycyclic musks.     

Polycyclic musks in green-lipped mussels (Perna viridis) from Hong Kong

Six polycyclic musk compounds [Cashmeran (DPMI), Celestolide (ADBI), Phantolide (AHMI), Traseolide (ATII), Tonalide (AHTN), and Galaxolide (HHCB)] were analysed in marine green-lipped mussels (Perna viridis) from Hong Kong. ADBI, HHCB and AHTN were detected in almost all samples, while AHMI, ATII and DPMI were not detected. Concentrations of ADBI, HHCB and AHTN in mussels ranged from below detection limit–0.0743 (mean: 0.0246), 0.247–6.08 (mean: 1.15) and 0.0591–0.738 (mean: 0.190) mg/kg lipid weight, respectively. Mussels from two sampling sites in central Victoria Harbour contained the highest total polycyclic musk levels, suggesting that these waters are heavily influenced by domestic sewage. Concentrations of HHCB and AHTN detected in the mussel samples were the second highest and the highest levels, respectively, compared to global concentrations. A preliminary risk assessment indicated that HHCB and AHTN in mussels pose little or no threat to the health of shellfish consumers. Nevertheless, more comprehensive studies are required to further assess the ecological and human health risks associated with polycyclic musks.     

Organophosphates and Synthetic Musk Fragrances in Freshwater Streams in Hessen/Germany

Four small freshwater river systems in Hessen, Germany, have been investigated with respect to seasonal and spatial concentration variations and transported load of the organophosphates tri‐n‐butyl phosphate (TBP), tris(2‐butoxyethyl)phosphate (TBEP), tris(2‐chloroethyl)phosphate (TCEP), tris(1‐chloro‐2‐propyl)phosphate (TCPP), and tris(1,3‐dichloro‐2‐propyl)phosphate (TDCPP) and the synthetic musk fragrances 1,3,4,6,7,8‐hexahydro‐4,6,6,7,8,8‐hexa‐methylcyclopenta‐[γ]‐2‐benzopyran (HHCB) and 7‐acetyl‐1,1,3,4,4,6‐hexamethyl‐1,2,3,4‐tetrahydronaphthalene (AHTN). Data originate from water samples collected in the time span from September 2003 to April 2005 at 25 sampling locations. The detection frequency for all compounds was about 90%. Mean concentration levels of organophosphates were 502 ng/L (TCPP), 276 ng/L (TBP), 183 ng/L (TBEP), 118 ng/L (TCEP), and 117 ng/L (TDCPP). The synthetic musk fragrances HHCB and ATHN were detected with mean concentrations of 141 and 46 ng/L, respectively. The variability of the concentration of all compounds was high with respect to space and time. The highest concentrations were observed in the Schwarzbach system characterized by the highest proportion of wastewater compared to the other river systems. Concentration levels of synthetic musk fragrances were significantly lower in summer times compared to winter times.     

Screening level ecological risk assessment for synthetic musks in surface water of Lake Taihu, China

A total of thirty-three surface water samples were collected from Meiliang Bay, Gonghu Bay and Xukou Bay of Lake Taihu, and analyzed for synthetic musks, including 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-[γ]-2-benzopyrane (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), 1-tert-butyl-3,5-dimethyl-2,5-dinitro-4-acetylbenzene (MK) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (MX). Ecological risks of these compounds were characterized by hazard quotient (HQ) method due to a lack of sufficient available toxicity data of synthetic musks. HHCB was the main synthetic musk detected in Lake Taihu, followed by AHTN, MK, and MX. The risk assessment results indicate that low ecological risks were posed by HHCB and total synthetic musks, and even lower risks posed by other synthetic musks in the worst case; much lower ecological risks were caused by both individual and total synthetic musks in the general case. The combined ecological risk from total synthetic musks calculation suggests that the combined ecological risk from all four synthetic musks was expected to be slightly higher than for the individual musks due to their joint action. The HQ spatial distribution maps show that several hot-spot areas were mainly around the river inlets to Lake Taihu, indicating that synthetic musks may be transported to Lake Taihu with municipal sewage and industrial wastewater from surrounding areas. However, the ecological risks in hot-spot areas posed by individual and total synthetic musks were still acceptable.     

Occurrence and accumulation features of polycyclic aromatic hydrocarbons and synthetic musk compounds in finless porpoises (Neophocaena phocaenoides) from Korean coastal waters

Reports of the occurrence and accumulation patterns of polycyclic aromatic hydrocarbons (PAHs) and synthetic musk compounds (SMCs) in marine mammals are scarce. In this study, the concentrations and accumulation profiles of PAHs and SMCs were determined in blubber from finless porpoises in Korean coastal waters. Total concentrations of PAHs and SMCs ranged from 6.0 to 432 (mean: 160) ng/g lipid weight and from 17 to 144 (mean: 52) ng/g lipid weight, respectively. Residue levels of PAHs were lower than those reported from other studies, while residue levels of SMCs were relatively higher than those reported in other studies. Naphthalene was the most abundant PAH and HHCB was the dominant SMC observed in finless porpoises. The concentrations of PAHs and SMCs were not correlated with each other, but were significantly correlated within the same chemical groups. No correlations were found between body size and residue levels of PAHs and SMCs.     

Ponderomotive effects in magnetospheric hydromagnetic waves

The ponderomotive force (PMF) is a ubiquitous nonlinear wave effect arising in plasma physics when applied wave fields or plasma parameters have significant spatial gradients. Some basic properties of the PMF are described as they relate to ULF hydromagnetic waves in the magnetosphere. Examples are given of recent results obtained using both analytical and numerical techniques for waves from the lowest frequencies (determined by the dimensions of the magnetosphere) up to the vicinity of the ion cyclotron frequency. These results include the possibilities that the PMF may transport plasma over large distances in the magnetosphere, and that the PMF may energize magnetospheric ions significantly. In particular the PMF may play a role in transporting and energizing O⁺ ions from the ionosphere into the body of the magnetosphere. The PMF can also generate nonlinear coupling between the slow magnetosonic mode and the other hydromagnetic modes. This should lead to limitation of density enhancements and, notably in the case of standing Alfvén waves, to spatial harmonic generation, secularly growing frequency shifts, and saturation of driven wave fields. Some implications of these results for the magnetosphere are discussed.Based on an invited review given in IAGA Symposium 3.07, Nonlinear and Kinetic Effects in ULF Waves, at the IUGG XXI General Assembly, Boulder, Colorado, July 2-14, 1995.     

Assessment of deterministic PMF modelling approaches

Probable maximum flood (PMF) event estimation has challenged the scientific community for many years. Although the concept of the PMF is often applied, there is no consensus on the methods that should be applied to estimate it. In PMF estimation, the spatio-temporal representation of the probable maximum precipitation (PMP) as well as the choice of modelling approach is often not theoretically founded. Moreover, it is not clear how these choices influence PMF estimation itself. In this study, combinations of three different spatio-temporal PMP representations and three different modelling approaches are applied to determine the PMF of a mesoscale basin keeping the antecedent catchment conditions and the total precipitation amount constant. The nine resulting PMF estimations are used to evaluate each combination of methods. The results show that basic methods allow for a rough estimation of the PMF. In cases where a physically plausible and reliable estimation is required, sophisticated PMP and PMF estimation approaches are recommended.

EDITOR D. Koutsoyiannis; ASSOCIATE EDITOR A. Viglione     

Zoosporic aquatic fungi growing on avian excrements in various types of water bodies

Coprophilic fungi in the water from six different water bodies were studied between 1995–1997. For hydrochemical analysis samples of water were collected every three months while for estimation of fungus content every month. Excrements of 3 phytophagous (greylag goose, roman-nosed goose, mute swan), 4 carnivorous (grey heron, white stork, marsh harrier, cormorant) and 3 omnivorous bird species (musk-duck, mallard, black-headed gull) were used as bait.

Thirty-six fungus species growing on avian excrements in the water of all examined water bodies were found, 6 of these species belonged to Chytridiomycetes and 30 to Oomycetes. The largest number of fungus species was detected on excrements of musk duck, mallard and mute swan, the smallest one on excrements of roman-nosed goose, marsh harrier and cormorant. Such fungus species as Achlya americana, Aphanomyces laevis, Dictyuchus monosporus, Pythium debaryanum, Pythium rostratum, Saprolegnia asterophora, Saprolegnia ferax and Saprolegnia parasitica were detected on excrements of all birds examined. Out of these 36 species, 11 are known as parasites or necrotrophs of fish. Rhizophydium ampullaceum and Diasporangium jonesianum are reported for the first time from Poland.     

Emission sources and health risk assessment of polycyclic aromatic hydrocarbons in ambient air during heating and non-heating periods in the city of Novi Sad,Serbia

The paper presents the assessment of emission sources and health risk of 16 PAHs in the city of Novi Sad, Serbia, with developed oil, food, chemical and cement industry. Although the observed region has been previously studied with regard to the occurrence of PAHs in ambient air, the sources of emission and health risk using multivariate statistical methods have never been studied before. The research was conducted during the heating and non-heating periods at three sampling sites located in industrial, residential and high-traffic area. The samples were collected by high-volume air sampler and analysed using the GC/MS system. The data were processed using the positive matrix factorization (PMF) and cluster analysis. To assess the cancer-risk of PAHs, potency equivalency factor approach was used. The results of PMF analysis have indicated that significant sources of PAH emissions are industrial processes and diesel combustion during the non-heating, and coal combustion, heating plants and diesel combustion during the heating season. Cluster analysis of experimental data has confirmed the results obtained using the PMF method. Estimated values of lifetime lung cancer risk were higher than those set by the World Health Organization and US Environmental Protection Agency which indicates that cancer risk due to exposure to PAHs in ambient air exists in both time periods on the territory of Novi Sad.     

Use of an Artificial Sweetener to Identify Sources of Groundwater Nitrate Contamination

The artificial sweetener acesulfame (ACE) is a potentially useful tracer of waste water contamination in groundwater. In this study, ACE concentrations were measured in waste water and impacted groundwater at 12 septic system sites in Ontario, Canada. All samples of septic tank effluent (n = 37) had ACE >6 µg/L, all samples of groundwater from the proximal plume zones (n = 93) had ACE >1 µg/L and, almost all samples from the distal plume zones had ACE >2 µg/L. Mean mass ratios of total inorganic nitrogen/ACE at the 12 sites ranged from 680 to 3500 for the tank and proximal plume samples. At five sites, decreasing ratio values in the distal zones indicated nitrogen attenuation. These ratios were applied to three aquifers in Canada that are nitrate‐stressed and an urban stream where septic systems are present nearby to estimate the amount of waste water nitrate contamination. At the three aquifer locations that are agricultural, low ACE values (<0.02‐0.15 µg/L) indicated that waste water contributed <15% of the nitrate in most samples. In groundwater discharging to the urban stream, much higher ACE values (0.2‐11 µg/L) indicated that waste water was the likely source of >50% of the nitrate in most samples. This study confirms that ACE is a powerful tracer and demonstrates its use as a diagnostic tool for establishing whether waste water is a significant contributor to groundwater contamination or not.     

Pesticide contamination of the coastline of Martinique

In January and February 2002, the presence of certain agricultural pesticides throughout the coastline of the Caribbean island of Martinique was investigated. The tropical climate of the French West Indies is suitable for banana production, which requires intensive use of pesticides. An inventory of all pesticides used on the island (compounds and tonnage) was compiled. Surveys and analyses revealed the presence of pesticides in the plumes of seven rivers. The organochlorine chlordecone and metabolites of aldicarb were detected at nearly all of the monitored sites, even though the use of chlordecone has been prohibited since 1993. Two triazines (ametryn and simazine) were also identified. The concentrations of carbamates and triazines detected in the water and sediment samples from Martinique are comparable to those reported for mainland France. Chlordecone concentrations in the sediment and particulate matter samples were, however, particularly high in the samples from Martinique. Toxicological implications are discussed. Of particular concern are the high levels of chlordecone (which is bioaccumulating and carcinogenic) and further monitoring of this compound is recommended, especially in fish and other sea-food products.     

A Bayesian approach for estimating extreme flood probabilities with upper-bounded distribution functions

Some recent research on fluvial processes suggests the idea that some hydrological variables, such as flood flows, are upper-bounded. However, most probability distributions that are currently employed in flood frequency analysis are unbounded to the right. This paper describes an exploratory study on the joint use of an upper-bounded probability distribution and non-systematic flood information, within a Bayesian framework. Accordingly, the current PMF maximum discharge appears as a reference value and a reasonable estimate of the upper-bound for maximum flows, despite the fact that PMF determination is not unequivocal and depends strongly on the available data. In the Bayesian context, the uncertainty on the PMF can be included into the analysis by considering an appropriate prior distribution for the maximum flows. In the sequence, systematic flood records, historical floods, and paleofloods can be included into a compound likelihood function which is then used to update the prior information on the upper-bound. By combining a prior distribution describing the uncertainties of PMF estimates along with various sources of flood data into a unified Bayesian approach, the expectation is to obtain improved estimates of the upper-bound. The application example was conducted with flood data from the American river basin, near the Folsom reservoir, in California, USA. The results show that it is possible to put together concepts that appear to be incompatible: the deterministic estimate of PMF, taken as a theoretical limit for floods, and the frequency analysis of maximum flows, with the inclusion of non-systematic data. As compared to conventional analysis, the combination of these two concepts within the logical context of Bayesian theory, contributes an advance towards more reliable estimates of extreme floods.     

The sources of the upper and lower halocline water in the Canada Basin derived from isotopic tracers

The Arctic Ocean is almost entirely surrounded by land, with shallow openings to the Pacific through Bering Strait (~ 45 m deep) and to the Atlantic through the Barents Sea (~50—450 m deep) and Fram Strait where the sill depth is around 2500 m. The bathy…     

Biochemical genetic study of European whitefish (Coregonus lavaretus) in Lake Mondsee,Upper Austria

Mature coregonids of Lake Mondsee were caught during spawning time on three known spawning sites. The aim of the study was to reveal whether the three stocks are reproductively isolated, and in consequence to decide whether they should be managed as separate stocks or as one panmictic population.Fish were examined morphologically and their tissue samples were examined electrophoretically for the enzyme products of 37 genetic loci.The gill-raker numbers (28–40) and electrophoretic alleles were typical for European whitefish,Coregonus lavaretus. No genetic differentiation (Nei's genetic distance D = 0.000) was found between the three samples studied. The genetic characteristics of the Lake Mondsee whitefish population, based on pooled genetic data, was compared to several other European whitefish populations. The average heterozygosity (6.5%) was high as usually in whitefish; genetic distances between the Lake Mondsee and three other European whitefish populations were within the range reported for the geographically distant populations of the species. Management implications of the results are briefly discussed.Contribution No. 21 in the Program of Joint Investigation of Holarctic Fishes among Russia, Canada, Finland, and Poland     

Pharmaceuticals and Other Organic Waste Water Contaminants Within a Leachate Plume Downgradient of a Municipal Landfill

Ground water samples collected from the Norman Landfill research site in central Oklahoma were analyzed as part of the U.S. Geological Survey (USGS) Toxic Substances Hydrology Program's national reconnaissance of pharmaceuticals and other organic waste water contaminants (OWCs) in ground water. Five sites, four of which are located downgradient of the landfill, were sampled in 2000 and analyzed for 76 OWCs using four research methods developed by the USGS. OWCs were detected in water samples from all of the sites sampled, with 22 of the 76 OWCs being detected at least once. Cholesterol (a plant and animal steroid), was detected at all five sites and was the only compound detected in a well upgradient of the landfill. N,N-diethyltoluamide (DEBT used in insect repellent) and tri(2-chloroethyl) phosphate (fire-retardant) were detected in water samples from all four sites located within the landfill-derived leachate plume. The sites closest to the landfill had more detections and greater concentrations of each of the detected compounds than sites located farther away. Detection of multiple OWCs occurred in the four sites located within the leachate plume, with a minimum of four and a maximum of 17 OWCs detected. Because the landfill was established in the 1920s and closed in 1985, many compounds detected in the leachate plume were likely disposed of decades ago. These results indicate the potential for long-term persistence and transport of some OWCs in ground water.     

Heavy metals in particulate and colloidal matter from atmospheric deposition of urban Guangzhou,South China

Suspended particulate matter (SPM) and colloidal matter (COM) in annual dry and wet deposition samples in urban Guangzhou were for the first time collected, and their trace metals were investigated by using inductively coupled plasma mass spectrometry (ICP-MS). The deposition flux of SPM and of metal elements varied largely among the investigated seasons, and reached the maximum in spring. The correlation analysis indicated that significant correlations existed among some of the metal elements in the deposition samples. The enrichment factors (EF) of metals in COM in the deposition ranging from 79.66 to 130,000 were much higher than those of SPM ranging from 1.65 to 286.48, indicating the important role of COM. The factor analysis showed that emissions from street dust, non-ferrous metal production, and heavy fuel oil were major sources of the trace metals. Positive matrix factorization (PMF) model was used to quantitatively estimate anthropogenic source.     

Evaluating hydro-mechanical interactions of adjacent clay-based sealing materials

Canada’s Nuclear Waste Management Organization (NWMO) is investigating various geological isolation concepts for Canada’s used reactor fuel (NWMO, 2005). These options are all based on the concept of multiple barriers that include Highly Compacted Bentonite (HCB), Dense Backfill (DBF), Light Backfill (LBF), and Gap Fill (GF). The hydraulic, mechanical, and other characteristics of these clay-based sealing materials have been examined previously, but typically in relative isolation (e.g., Dixon, 1999, Blatz, 2000, Siemens, 2006, Stroes-Gascoyne et al., 2006, Baumgartner et al., 2007). Information on how these clay-based sealing materials interact with each other is needed to understand the evolution and performance of the overall sealing system.A total of twenty-three (23) tests that examine the physical interaction of physically dissimilar clay-based sealing materials were installed and monitored at Atomic Energy of Canada Limited’s (AECL) geotechnical laboratory. This paper describes the process of water uptake, interaction between the components installed, and the role of groundwater salinity on water uptake as interpreted from these tests.     

Long-Term Ground Water Quality Impacts from the Use of Hexazinone for the Commercial Production of Lowbush Blueberries

Lowbush blueberries, native to eastern Canada and Maine, are an important economic crop in these areas. Herbicides containing the active ingredient hexazinone are commonly applied to blueberry fields, and there is a high frequency of detection of relatively low concentrations of hexazinone in domestic wells located close to areas of lowbush blueberry production. The objective of this study was to determine the long-term impacts from hexazinone-based herbicide use on ground water quality in the immediate growing areas.
Physical and chemical hydrogeologic data were collected for an outwash sand and gravel aquifer in southwestern New Brunswick, Canada. The majority of the land overlying the aquifer is devoted to lowbush blueberry production. Twenty-one nested monitoring wells were sampled for hexazinone and hexazinone metabolites over a four-year period. Hexazinone was consistently detected at values of 1 to 8 parts per billion (ppb) in all but two of these wells, one that is upgradient of herbicide applications, and one that is downgradient with anoxic conditions. Hexazinone metabolites B and A1 were also detected in all but two of the 21 wells at values ranging from 0.5 to 2.5 ppb. The hexazinone and metabolite data suggest both aerobic and anaerobic degradation of hexazinone. Complete degradation of hexazinone appears to occur only in the one downgradient well exhibiting anoxic ground water conditions. Concentrations of hexazinone and its metabolites in the ground water were essentially constant over the four-year period.