Critical evaluation of the measurement of the 1- octanol / water partition coefficient of hydrophobic compounds

Data on the experimental measurement of the octanol/water partition coefficient (K_ow) with hydrophobic compounds was assembled from the literature. The precision, characterised by the standard deviation of mean K_ow values based on five commonly used experimental methods, over an extended K_ow range was found to generally decline with compounds having log K_ow > 5.5. In the log K_ow range from 2.0 to 5.5 there was little difference between the mean values of log K_ow determined by the different methods but major differences occured with compounds having log K_ow > 5.5. The agreement between calculated ClogP values and K_ow values derived from individual experimental methods indicated that ClogP overestimates log K_ow from all experimental methods with compounds having values greater than 5.5.     

Stable isotope determination in wild and farmed gilthead sea bream (Sparus aurata) tissues from the western Mediterranean

Stable isotopes of carbon and nitrogen (delta(13)C and delta(15)N) have been determined in wild and farmed gilthead sea bream (Sparus aurata) samples of white and red muscle, liver, gills and gonads. First, delta(13)C and delta(15)N values were determined in samples with and without lipid removal to check the possible effect of lipid content on the stable isotope values of the different tissues studied. Differences were found for delta(13)C in all tissues studied apart from white muscle of wild fish, the tissue with the lowest lipid content. For delta(15)N values no differences were found in wild fish tissues. Liver from farmed fish showed lower delta(15)N value after lipid removing. Further conclusions were based on results obtained from lipid-free samples. delta(13)C of cultured fish tissues showed a mean depletion of 2.9+/-0.4 per thousand compared to wild specimens, suggesting different sources of carbon in the diet, probably due to the feed used during sea-cage culture. Cultured gilthead sea bream tissues were significantly more enriched in nitrogen than wild specimens by an average of 1.5+/-0.2 per thousand in white muscle, indicating a slight increase in the trophic level. Determination of stable isotope signatures of gilthead sea bream tissues allows clear discrimination between wild and cultured sea bream, and characterisation of differences in diet and feeding conditions in any tissue studied.     

Biomonitoring of persistent organochlorine pesticides, PCDD/PCDFs and dioxin-like PCBs in blood of children from South West Germany (Baden-Wuerttemberg) from 1993 to 2003

In the context of a monitoring program, persistent organic pollutants (POPs) were quantified in the blood of 10 year old children at four different demographic regions in Baden-Wuerttemberg, a highly industrialised federal state in South West Germany. DDE, HCB, PCB 138, PCB 153 and PCB 180 were measured in 1996/1997, 1998/1999, 2000/2001 and 2002/2003 in individual samples of about 400 children per year. PCDD/PCDFs and some relevant coplanar PCBs were determined in pooled samples from children in seven cycles from 1993 to 2003. Blood concentrations of the investigated compounds decreased in that time period by a factor of 2-4 with the exception of most PCDFs. The concentrations of POPs in the blood of the children were distinctly lower than the concentrations reported for adults. Breast feeding was associated with about 30% higher median concentrations of DDE, HCB, PCBs and a 30% increase for mean PCDD/PCDF concentrations. Concerning demographic differences, significant lower concentrations of HCB, PCBs and PCDD/PCDFs could be seen in children from Mannheim compared to the region of Aulendorf. About 10-20% higher concentrations were found in boys compared to girls for HCB, indicator PCBs and PCDD/PCDFs. The pattern of non-ortho and mono-ortho PCBs in the blood of children was similar to the pattern reported for mother's milk, and PCB 126 and PCB 156 contributed about 70% to the toxicity of dioxin-like PCBs and about one-third to total TEQ including PCDD/PCDFs.     

Dissipation and sorption of six commonly used pesticides in two contrasting soils of New Zealand

We investigated dissipation and sorption of atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone in two contrasting New Zealand soils (0–10 cm and 40–50 cm) under controlled laboratory conditions. The six pesticides showed marked differences in their degradation rates in both top- and subsoils, and the estimated DT₅₀ values for the compounds were: 19–120 (atrazine), 10–36 (terbuthylazine), 12–46 (bromacil), 7–25 (diazinon), 8–92 (hexazinone) and 13–60 days for procymidone. Diazinon had the lowest range for DT₅₀ values, while bromacil and hexazinone gave the highest DT₅₀ values under any given condition on any soil type. Batch derived effective distribution coefficient (K _d ^eff) values for the pesticides varied markedly with bromacil and hexazinone exhibiting low sorption affinity for the soils at either depth, while diazinon gave high sorption values. Comparison of pesticide degradation in sterile and non-sterile soils suggests that microbial degradation was the major dissipation pathway for all six compounds, although little influence of abiotic degradation was noticeable for diazinon and procymidone.     

Simultaneous presence of DDT and pyrethroid residues in human breast milk from a malaria endemic area in South Africa

DDT and pyrethroids were determined in 152 breast-milk samples from three towns in KwaZulu-Natal, South Africa, one of which had no need for DDT for malaria control. All compounds were found present in breast milk. Primiparae from one town had the highest mean SigmaDDT whole milk levels (238.23 microg/l), and multiparae from the same town had the highest means for permethrin (14.51 microg/l), cyfluthrin (41.74 microg/l), cypermethrin (4.24 microg/l), deltamethrin (8.39 microg/l), and Sigmapyrethroid (31.5 microg/l), most likely derived from agriculture. The ADI for DDT was only exceeded by infants from one town, but the ADI for pyrethroids was not exceeded. Since the ADI for DDT was recently reduced from 20 to 10 microg/kg/bw, we suggest that this aspect be treated with concern. We therefore raise a concern based on toxicant interactions, due to the presence of four different pyrethroids and DDT. Breastfeeding however, remains safe under prevailing conditions.     

PAHs, PCDD/Fs, PCBs and HCB in leaves from Brisbane, Australia

The concentrations of SOCs in leaves of an evergreen Australian native tree (Melaleuca leucadendra) and grass collected in Brisbane, Australia were determined. The concentrations of PCDD/Fs and PAHs in the leaf tissue were comparable to those reported for urbanised areas in other industrialised countries. A distinct difference in the compound profiles between the leaves of the two species was observed, with higher concentrations of the lower molecular mass PAHs and PCDD/Fs and lower concentrations of the higher molecular mass PAHs and PCDD/Fs in the Melaleuca leaves relative to the grass leaves. The interspecies differences are explained on the basis of the larger size of the lipophilic compartment (for compounds with low K(OA)) and the lower ratio of surface area to volume in the Melaleuca leaves.     

Metal levels in body tissues, forage and fecal pellets of elk (Cervus elaphus) living near the ore smelters at Sudbury, Ontario.

Ontario's only free-ranging elk herd located at Burwash-French River has been subjected to the influence of historic copper-nickel-iron (Cu-Ni-Fe) ore smelting operations within the Sudbury area. Metal levels in selected body tissues, preferred forage items and fecal pellets were determined, and their potential effects on health and reproductive viability assessed. Significant age effects were apparent in 13 out of 31 tissue metal values obtained, with most age-related differences attributable to elevated concentrations in fetal tissues. Cu and zinc (Zn) levels were four to six times higher in livers and one and a half to two times higher in the bones of fetuses as compared to post-natal animals. Enhanced pre-natal tissue burdens were also noted for cobalt (Co), Ni and lead (Pb) in muscles. However, mean cadmium (Cd) levels in kidney, liver and muscle tissues, as well as hepatic Fe concentrations, showed significant increases with age. Although Cd levels in the kidneys of older elk were still well below the reported threshold for irreversible organ damage, and not considered to be health-threatening, detailed histological study of the cortical tissues for subtle pathotoxicological effects may be warranted. Unlike renal and hepatic tissues, Cd concentrations in skeletal muscle were minimal and within levels considered acceptable for human consumption. Forage species collected in the elk range generally showed higher (two to eight times) Ni and Fe levels than the corresponding plants from a non-contaminated reference site. The highest Ni and Fe burdens were carried by eastern white cedar, a preferred winter food item for elk. No consistent site-related trends were demonstrated by Cu, Zn, Co, Pb, chromium (Cr) and Cd forage levels. Mean metal concentrations in fecal pellets generally exceeded the mean composite forage levels by a factor of 3, except for Ni, which was five times more concentrated in feces. Significantly elevated Ni and Fe levels in preferred browse species and fecal pellets of the Sudbury-area elk could be of concern and warrant further investigation.     

Contamination of butyltin compounds in Malaysian marine environments

Concentration of butyltin compounds (BTs), including tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) and total tin (SigmaSn) were determined in green mussel (Perna viridis), 10 species of muscle fish and sediment from coastal waters of Malaysia. BTs were detected in all these samples ranging from 3.6 to 900 ng/g wet wt., 3.6 to 210 ng/g wet wt., and 18 to 1400 ng/g dry wt. for mussels, fish and sediments, respectively. The concentrations of BTs in several locations of this study were comparable with the reported values from some developed countries and highest among Asian developing nations. Considerable concentration of BTs in several locations might have ecotoxicological consequences and may cause concern to human health. The parent compound TBT was found to be highest than those of its degradation compounds, DBT and MBT, suggesting recent input of TBT to the Malaysian marine environment. Significant positive correlation (Spearman rank correlation: r2=0.82, P<0.0001) was found between BTs and SigmaSn, implying considerable anthropogenic input of butyltin compounds to total tin contamination levels. Enormous boating activities may be a major source of BTs in this country, although aquaculture activities may not be ignored.     

Butyltins in muscle and liver of fish collected from certain Asian and Oceanian countries

Concentrations of butyltin residues were determined in muscle tissue of fish collected from local markets and sea food shops in India, Bangladesh, Thailand, Indonesia, Vietnam, Taiwan, Australia, Papua New Guinea and the Solomon Islands. Contamination levels were determined in the Asia-Pacific region and human exposure was estimated. Similarly, corresponding liver samples of fish muscle collected in Australia, Papua New Guinea and the Solomon Islands were analyzed to obtain information on partitioning of butyltin compounds between muscle and liver tissues. Butyltin compounds were detected in most of the samples which suggested widespread contamination in Asia and Oceania. The concentrations of butyltin compounds were, on average, an order of magnitude higher in liver than in muscle. Residue concentration of Sigmabutyltin in liver was found to be correlated significantly (p < 0.02) with those in muscle. Intensive ship-scrapping activities, sewage disposal and antifouling paints are considered the major sources of butyltins in this region. Increased proportions of MBT over DBT and TBT in samples from most locations indicated degradation of TBT to MBT in fish tissues during storage at 4 degrees C in the dark over 1-2 years. The possibility that fish have been subject to increased exposure to MBT and that TBT degrades to MBT quite rapidly in tropical environments are also considered. Butyltin concentrations in fish from Asia and Oceania were lower than those reported for Japan, Canada and the USA. Although the number of samples analyzed from each country was small, it is tentatively suggested that intake of butyltins by humans via consumption of fish in these countries was < 25% of the tolerable daily intake of 250 ng kg bw(-1) day(-1). To our knowledge, this is the first study reporting on butyltin pollution in developing Asian countries.     

Determination of PCDD/Fs and dioxin-like PCBs in fish oils for feed ingredients by congener-specific chemical analysis and CALUX bioassay

The present research was intended to determine the suitability of the CALUX assay as a screening method for dioxins in fish oil used as a feed ingredient in Japan. Alteration of TEQ in fish oil according to newly proposed toxic equivalency factors (TEF) is also discussed. In the analysis, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in 41 fish oil samples were determined by using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) and CALUX bioassay. The mean TEQ values derived from 1998 WHO-TEF of PCDD/Fs and DL-PCBs were 2.6 and 9.9 pg g(-1) (ww), respectively. The levels of TEQ derived from the recently re-evaluated 2005 WHO-TEF were slightly lower than those of the former in both groups. Notably, the contribution of mono-ortho DL-PCBs to total 2005 WHO-TEQ was considerably decreased compared to the case of 1998 WHO-TEQ, resulting from the reduction in its TEF values, while the non-ortho DL-PCBs contribution was increased. The mean TEQ determined by CALUX assay for PCDD/Fs was approximately three times higher, whereas DL-PCBs was approximately two times lower than WHO-TEQ determined by HRGC/HRMS; the sum of PCDD/Fs and DL-PCBs was very similar by both methods. The correlation coefficients of TEQ between the CALUX assay and HRGC/HRMS analysis were 0.84, 0.89, and 0.90 for PCDD/Fs, DL-PCBs, and the sum, respectively. These results suggest that the CALUX assay is a very useful method for the screening of dioxin-related compounds in fish oils.     

Response of mosses to the heavy metal deposition in Poland--an overview

Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) in Pleurozium schreberi (Brid.) Mitt., a common moss species, were used to indicate relative levels of atmospheric deposition in Poland in the years 1975-1998. Spatial and temporal differences in the heavy metal concentrations in mosses were found. The highest concentration of heavy metals was recorded in the moss samples from the southern, most industrialised part of the country, and the lowest from north-eastern Poland. A significant decrease of heavy metals over 20 years (1975-1998) was found.     

Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax)

In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.     

Trace metal concentrations and their distribution in the lobster Panulirus inflatus (Bouvier, 1895) from the Mexican Pacific coast

The concentration and distribution of Fe, Mn, Ni, Cu, Co, Cd, Cr and Zn among the tissues of female and male lobster Panulirus inflatus from the Pacific coast of México were determined. Distinct inter-tissue and intersize differences in metal concentrations were observed. In general, highest Zn concentrations were found in viscera while highest Cu levels occurred in the gill and gonadal material. The highest Mn, Ni, Cr and Co concentrations were observed in exoskeleton and highest in eggs and gills. Cadmium was undetectable (<0.05 microg g(-1)) in most tissues, only muscle and viscera contained low but detectable amounts. A positive relationship between size and metal concentration was observed only for Zn contained in the muscle of females and males, for Zn contained in the gonad of females, for Mn contained in the gonad of males and for Cu associated with muscle of males. These results are discussed with regard to trace metal concentrations found in temperate and tropical regions.     

Geographical variation of persistent organochlorine concentrations in blubber of ringed seal (Phoca hispida) from the Canadian Arctic: univariate and multivariate approaches

Geographical variation of organochlorine (OC) concentrations in ringed seal (Phoca hispida) in the Canadian Arctic was studied using univariate and multivariate statistical techniques. The dataset consisted of 80 individual OC components (58 PCB congeners plus DDT- and chlordane (CHL)-related compounds, toxaphene, hexachlorocyclohexanes (HCH), chlorobenzenes (CBz), and dieldrin) determined in 221 ringed seal blubber samples from 13 locations throughout the Canadian Arctic from the period 1983 to 1989. Mean concentrations of the major OC groups in ringed seal blubber (SigmaPCBs, SigmaDDT, SigmaCHL and toxaphene), adjusted for the age and sex of the seals, showed few significant geographical differences. Principal components analysis was used to examine geographical trends. Significant differences in mean factor scores for three of four principal components were found between sampling locations. Locations in the western and high Arctic could be distinguished from those in Hudson Bay by highest scores along principal component two which was associated principally with CBz. PCB congeners with six or more chlorine substitutions declined with increasing north latitude, whereas more volatile OCs (CBz, HCH, less chlorinated PCBs) increased in the proportion of total OCs with latitude. Proportions of less chlorinated PCBs also decreased with increasing longitude, whereas slopes of regressions for more highly chlorinated PCBs increased significantly. The results were generally consistent with the 'cold condensation' hypothesis of increasing proportions of more volatile OCs with increasing latitude and distance from sources.     

Exposure assessment for trace elements from consumption of marine fish in Southeast Asia

Concentrations of 20 trace elements were determined in muscle and liver of 34 species of marine fish collected from coastal areas of Cambodia, Indonesia, Malaysia and Thailand. Large regional difference was observed in the levels of trace elements in liver of one fish family (Carangidae): the highest mean concentration was observed in fish from the Malaysian coastal waters for V, Cr, Zn, Pb and Bi and those from the Java Sea side of Indonesia for Sn and Hg. To assess the health risk to the Southeast Asian populations from consumption of fish, intake rates of trace elements were estimated. Some marine fish showed Hg levels higher than the guideline values by U.S. Environmental Protection Agency and Joint FAO/WHO Expert Committee on Food Additives (JECFA). This suggests that consumption of these fish may be hazardous to the people.     

Weekday/Weekend differences in ambient air pollutant concentrations in atlanta and the southeastern United States

The authors quantified changes between mean weekday and weekend ambient concentrations of ozone (O3) precursors (volatile organic compounds [VOC], carbon monoxide [CO], nitric oxide, and oxides of nitrogen [NOx]) in Atlanta and surrounding areas to observe how weekend precursor emission levels influenced ambient O3 levels. The authors analyzed CO, nitric oxide (NO), and NO, measurements from 1998 to 2002 and speciated VOC from 1996 to 2003. They observed a strong weekend effect in the Atlanta region, with median daytime (6:00 a.m. to 3:00 p.m. Eastern Standard Time) decreases of 62%, 57%, and 31%, respectively, in the ambient levels of NO, NOx, and CO from Wednesdays to Sundays, during the ozone season (March to October). They also observed significant decreases in ambient VOC levels between Wednesdays and Sundays, with decreases of 28% for the sum of aromatic compounds and 19% for the sum of Photochemical Assessment Monitoring Stations target compounds. Despite large reductions in O3 precursor levels on weekends, day-of-week differences in O3 mixing ratios in and near Atlanta were much smaller. Averaging overall O3-season days, the 1-hr and 8-hr mean peak daily O3 maxima on Sundays were 4.5% and 2.3% lower, respectively, than their mean levels on Wednesdays (median of 14 site differences), with no sites showing statistically significant Wednesday-to-Sunday differences. When restricted to high-O3 days (highest 3 peak O3 days per day of week per site per year), the 1-hr and 8-hr Sunday O3 mixing ratios were 11% and 10% lower, respectively, than their mean peak levels on Wednesdays (median of 14 site differences), with 6 of 14 sites showing statistically significant Wednesday-to-Sunday differences. The analyses of weekday/weekend differences in O3 precursor concentrations show that different emission reductions than normally take place each weekend will be required to achieve major reductions in ambient ozone levels in the Atlanta area.     

Investigation of carbonyl compounds in air from various industrial emission sources

The emission concentrations of carbonyl compounds in air were quantified from a total of 195 man-made source units within 77 individual companies at a large industrial complex in Korea. The measurement data were evaluated both by absolute magnitude of concentration and by their relative contribution to malodor formation such as malodor degree (MD) derived from empirical formula. It was found that formaldehyde exhibited the highest mean concentration of 323ppb with a median value of 28.2ppb, while butyraldehyde recorded the highest contribution to odor formation with an MD value of 3.5 (186 (mean) and 9.8ppb (median)). The relative intensity of carbonyl emission, when compared by the sum of MD, showed the highest source strength from the food and beverage (industry sector) and scrubber (source unit). A comprehensive evaluation of the carbonyl data from diverse industrial facilities thus allowed us to describe the fundamental patterns of their emission.     

Spatial distribution of organotins in sediments of lowland river catchments

A method is described for the measurement of nanogram quantities of a range of methyl and butyltin compounds. The method utilises a modified purge and trap/boiling point separation technique for the determination of organotin compounds in sediment samples. A spatial survey of sediment samples within 5 river systems in the East Anglia region of the United Kingdom was undertaken and identified a range of organotin compounds with concentrations of tributyltin (TBT) ranging from <3.9 ng g(-1) up to 1291 ng g(-1). The highest values were found in areas connected with boating activities. Wherever TBT was present, dibutyltin and monobutyltin were most commonly found along with small concentrations of certain methyltins.     

Organochlorine pesticides and hexachlorobenzene in tissues of fish and invertebrates caught near a sewage outfall

Concentrations of organochlorine pesticides and hexachlorobenzene (HCB) were determined in 16 fish, 1 mollusc and 1 crustacean species living near a cliff-face sewage outfall. For the 15 organochlorine compounds scanned, HCB, chlordane, dieldrin and SigmaDDT were recorded in highest concentrations. There was considerable variation in concentrations between muscle and liver and between species. Livers had higher concentrations of organochlorines and a higher percentage lipid than muscle. The highest concentrations were recorded in livers of the elasmobranch and tetraodontiform fishes. Organochlorines were only recorded at low concentrations in muscle, often at or near detection limits. No organochlorines were detected in the two invertebrate species.     

Signs of a negative trend in the MODIS aerosol optical depth over the Southern Balkans

A negative trend is being revealed in the MODIS aerosol optical depth [AOD] observed over the Southern Balkan/Eastern Mediterranean region. Collection 005 MODIS/Terra and MODIS/Aqua AOD at 470 nm measurements were evaluated against Brewer ground-based measurements over Thessaloniki, Greece and CIMEL ground-based measurements of AOD over Heraklion, Crete. A detailed study of the monthly, seasonal and inter-annual variability of the MODIS/Terra and MODIS/Aqua AOD values over selected locations around the Balkan Peninsula showed that the higher mean AOD values occurred in the spring and summer months, whereas the lowest were found in the winter-time. For all seasons, the highest AODs were observed for the northern-most latitudes with a marked decrease towards the southern-most sites. A statistically significant decreasing trend in aerosol load in the region over all sites as derived from the MODIS/Terra measurements gave the highest per annum change seen for the summer months to be ?4.09 ± 2.34%, and the lowest for the winter months as ?2.55 ± 4.36%, which also shows the higher variability.