Influence of prefreezing on heavy metal concentrations in Bluegill sunfish

Concern for possible changes in tissue metal concentrations due to freezing of fish specimens prior to analysis prompted this investigation. Bluegill sunfish (Lepomis macrochirus) were collected from a Virginia stream and prepared for analysis of zinc, cadmium and lead concentrations either fresh or after 1, 7, and 70 days of freezing. Intact specimens as well as bone and liver tissue were then analyzed. Zinc concentrations displayed a statistically significant (P < 0.05) negative trend with duration of freezing in whole-body, liver and bone samples. Lead and cadmium concentrations showed no consistent pattern which could be related to length of the freezing period in any of the tissues analyzed. However, median concentrations of zinc, cadmium and lead were 10–30% lower in prefrozen sunfish (aggregated over freezing periods) than in sunfish which were analyzed fresh in seven of the eight tissue-metal combinations examined. These results indicate that freezing of sunfish prior to sample preparation can depress metal concentrations in both tissues and whole fish. Programs to monitor heavy metal contamination in sunfish and other fishes may incur bias unless specimens are prepared for analysis fresh or all samples experience equivalent freezing regimes.     

Fish tissue quality in near-coastal areas of the Gulf of Mexico receiving point source discharges

The objective of this study was to determine inorganic and organic contaminant concentrations in edible tissue of fish collected from eight coastal areas receiving wastewater discharges and from two reference locations. Trace metal residues were statistically similar regardless of the collection site. Zinc (100% detection in all samples), total mercury (100%), total arsenic (92%), copper (92%), and selenium (88%) were the more commonly detected trace metals. Mercury concentrations exceeded the Florida health-based standard of 0.5 microg/g for limited fish consumption in 30% of the total samples and averaged 0.40 (+/- 1 S.D. = 0.22, range < or = 0.08 to 0.85) microg/g wet weight. The average total PAH concentrations were 1.79 (+/- 1.60) ng/g (reference areas) and 2.17 (+/- 3.29) ng/g (wastewater-impacted areas). Pyrene was detected most frequently (63% of the total samples) and averaged 0.74 (+/- 0.35) ng/g wet wt. The average total PCB concentrations were 4.8 (+/- 7.1) ng/g (reference areas) and 31.6 (+/- 31.3) ng/g (wastewater-impacted areas) Concentrations of dieldrin and cis-chlordane were approximately eight times greater, respectively, in fish collected from wastewater receiving waters, whereas total DDT and total pesticide concentrations were not elevated in the same areas. Concentrations of total PCBs and all chlorinated pesticides were below US health-based standards. The lack of a published reference data base for fish tissue quality in near-coastal areas of the Gulf of Mexico restricts an assessment of the environmental significance of results from this and similar studies investigating the fate of point source contaminants.     

Trace metals and organochlorines in the bamboo shark Chiloscyllium plagiosum from the southern waters of Hong Kong, China

The bamboo shark Chiloscyllium plagiosum is an abundant benthic species along the shallow continental shelf of Southeast Asia. It is commonly taken by fishermen in China, India, Taiwan and Thailand for human consumption. This study measured trace metal and organochlorine concentrations in C. plagiosum collected from the southern waters of Hong Kong, China. Metals (Ag, Cd, Cr, Cu, Mn, Ni, Pb and Zn) were measured in three different tissues: dorsal muscle, spleen and liver. Polychlorinated biphenyls (PCBs) and chlorinated pesticides in the dorsal muscle were identified and quantified using gas chromatography. Metal concentrations varied among the three different tissues, with liver having higher levels of Ag and Cd, and spleen possessing higher levels of Cu and Mn. Both Ni and Pb in all tissues were below the detection limit. Tissue concentrations of Cr, Cu, Mn and Zn generally decreased with increasing body weight whilst no significant concentration-size relationship was found for other metals. In muscle tissues, total PCBs ranged from 1.056-4.771 ng/g (wet wt.) with a median of 1.801 ng/g, while total DDTs ranged from 0.602-23.55 ng/g with a median of 1.109 ng/g, in which p,p'-DDE was the predominant metabolite. Levels of total hexachlorohexanes and cyclodienes were low. The pesticide p,p'-DDT was the only compound found to be positively correlated with body weight, indicating temporal bioaccumulation of this compound. Zn concentrations in the muscle of C. plagiosum were comparatively higher than recorded in other shark species, however, concentrations of other metals and organochlorines were relatively low. C. plagiosum feeds primarily on polychaetes, shrimps and small fishes, and thus is unlikely to contain levels of contaminants of human health concern.     

Metal profiles used as environmental markers of green turtle (Chelonia mydas) foraging resources

The Baja California Peninsula, Mexico serves an important role for feeding and developing sea turtles. High concentrations of metals detected in green turtles (Chelonia mydas) from Magdalena Bay prompted an investigation into the sources of metals in the region. We compared metal concentrations in sea turtle tissues with plant species found in their stomach contents, and with the same species of plants collected inside a sea turtle refuge area known as Estero Banderitas. Differences in the metal concentrations between marine plant species were minimal. Principal components analysis of the percent contribution of individual metals to the overall metal signature of each plant or tissue sample generated three principal components that explained 80.7% of the total variance in the data. The plant samples collected within Estero Banderitas formed a separate grouping from the green turtle tissue samples and the plants from the stomach contents. The plants in the stomach contents contained greater percent contributions of Cd and Zn than the plants collected inside the bay, while Pb and Mn contributed more to the metal profiles in the bay samples. The metal profiles in the sea turtle tissues more closely resembled the stomach contents than the same species of plants collected within Estero Banderitas, and suggest that sea turtles collected inside Magdalena Bay use foraging resources outside of the Estero Banderitas region. This work supports the suggestion that metal profiles can be used as "environmentally acquired markers" to improve our understanding of the extent of sea turtle foraging areas.     

The influence of soil characteristics on the extractability of Cd, Pb and Zn in upland and moorland soils

A study was undertaken to investigate the feasibility of using existing data sets of total soil metal concentrations and soil parameters, such as pH, to predict available metal concentrations on a regional or national basis. The attraction of such an approach is that it would provide valuable data for initiatives requiring information on the availability and mobility of metals in soils without the need for costly soil sampling and analysis. Ninety-seven topsoil and subsoil samples were collected from 6 soil series in a catenary sequence in north Wales to provide data for the development of an empirical model. These were analysed for total, 0.01 M CaCl2-extractable and porewater metal concentrations and for a range of soil properties including pH, solid and dissolved organic matter and cation exchange capacity. Regression analysis showed that, of the soil parameters measured, pH was the most important predictor variable for the estimation of CaCl2-extractable Cd, Pb and Zn. pH accounted for up to 86% of the variance in the proportion of 'total' metals which were extracted by CaCl2, a reagent that is commonly used to estimate plant uptake of elements. However, the relationships recorded between soil parameters and Kd (total metal/porewater metal) were much weaker, indicating that porewater metal concentrations can less readily be predicted from total soil metal concentrations and soil properties.     

Accumulation de quelques metaux lourds (Cd,Cu, Pb et Zn) chez l'eperlan (Osmerus mordax) preleve sur la rive Nord de l'Estuaire du Saint-LaurentHeavy metal accumulation (Cd,Cu, Pb and Zn) by smelt (Osmerus mordax) from the North shore of the St Lawrence estuary

Heavy metals in trace amounts are normal constituents of marine organisms. At sufficiently high concentrations, heavy metals are toxic to living organisms and so it is important to know by how much their concentration may be increased before effects on marine or estuarine populations can be detected or commercial species become unsuitable as food. A method of removing metals is by storage in a particular tissue. Several different sites for storing metals were investigated and concentrations of Cd, Cu, Pb and Zn were examined in muscle, liver and gonads of the smelt (Osmerus mordax) from the North shore of the St Lawrence estuary. Copper and zinc are constituents of several enzymes and are absolutely essential for normal growth and development, while cadmium and lead are not known to have necessary physiological function. A modified wet digestion procedure was used to prepare biological samples for the determination of trace elements by flameless atomic absorption spectrophotometry procedure, using calibration standards made up in a matrix of similar acidity (Table 1). NBS reference material bovine liver was analyzed along with the samples and the results were within the specified tolerance (Table 2). Analyses were reported on a dry weight basis (Table 3) and the correlations with total body weight were determined by regression analysis. Copper (range 0.3–3.3 μg g^?1) and zinc (range 19–38 μg g^?1) in muscle fillets were found to be negatively correlated with total body weight (Fig. 1). Apparent decreasing concentrations in these two metal levels in muscle sample with increasing body weight were possibly due to factor such as dilution with growth. Growth may dilute metal concentrations in an organism if tissue is added faster than metal. Livers and gonads contained greater levels of the four metals than somatic muscle. Liver metal concentrations of Zn (range 29–108 μg g^?1) and Cd (range 0.06–0.37 μg g^?1) increased with total body weight. All equations fit data at P < 0.01 (Fig. 2). Positive correlations between size and metal concentrations suggest that net uptake may occur. Inessential, slowly exchanging metals such as Cd appear to reflect an uptake which tend to become a cumulative process (age dependence of concentrations). The occurrence of insignificant correlation between liver concentrations of Cu (mean value: 4 μg g^?1) and environmental concentrations of this metal was consistent with equilibration. Since fish are known to possess the metal binding protein metallothionein, a sequestering agent, detoxification of these metals in fish liver may be by sequestration rather than elimination. Increasing metal concentrations in liver may represent storage of sequestered products in that organ. In the gonads, no significant relationship exists between total body weight and trace metal contents. Results of t-test indicated that females had significantly greater Cu and Zn concentrations, but no significant difference existed between males and females for Cd concentrations (Figs 3 and 4). Thus, the relation between concentration and total body weight appears to be specific as to the species, tissues analyzed and environmental conditions. The comparison of metal concentrations in fish to assess variations in contamination levels requires understanding the relationship between metal concentration and body size within each population.     

Particle size distribution and atmospheric metals measurements in a rural area in the South Eastern USA

Atmospheric particle mass concentrations were measured at a site adjacent to Lake Hartwell, GA, during six dry sampling events in February-March 2003. The overall average PM2.5 mass concentration was 9.5 microg/m3 and the overall average total suspended particles mass concentration was 19.1 microg/m3. Particulate matter was collected on a deposition plate mounted onto a specially designed wind vane and was subsequently analyzed to determine the particle size distribution. The average geometric particle diameter was found to be 2.8 microm. Particulate matter collected was found to be closely approximately at log-normal distribution, with a count median diameter of 1.5 mum and a geometric standard deviation of 1.8. Individual metal concentrations present in airborne particulate matter were determined for cadmium, chromium, copper, iron, lead, manganese, nickel, and zinc using inductively coupled plasma-mass spectrometry analysis of samples collected on Teflon filters. Ambient metal concentrations were found to range from 0.8 ng/m3 for cadmium to 512 ng/m3 for iron. The dry deposition flux of metals was estimated to be in the range of 0.17 mg/(m2 year) for cadmium to 102 mg/(m2 year) for iron. More samples need to be collected and analyzed, both temporally and spatially, in order to establish atmospheric metals fluxes onto surfaces.     

Accumulation de quelques metaux lourds (Cd, Cu, Pb et Zn) chez l'eperlan (Osmerus mordax) preleve sur la rive Nord de l'Estuaire du Saint-Laurent

Heavy metals in trace amounts are normal constituents of marine organisms. At sufficiently high concentrations, heavy metals are toxic to living organisms and so it is important to know by how much their concentration may be increased before effects on marine or estuarine populations can be detected or commercial species become unsuitable as food. A method of removing metals is by storage in a particular tissue. Several different sites for storing metals were investigated and concentrations of Cd, Cu, Pb and Zn were examined in muscle, liver and gonads of the smelt (Osmerus mordax) from the North shore of the St Lawrence estuary. Copper and zinc are constituents of several enzymes and are absolutely essential for normal growth and development, while cadmium and lead are not known to have necessary physiological function. A modified wet digestion procedure was used to prepare biological samples for the determination of trace elements by flameless atomic absorption spectrophotometry procedure, using calibration standards made up in a matrix of similar acidity (Table 1). NBS reference material bovine liver was analyzed along with the samples and the results were within the specified tolerance (Table 2). Analyses were reported on a dry weight basis (Table 3) and the correlations with total body weight were determined by regression analysis. Copper (range 0.3–3.3 μg g⁻¹) and zinc (range 19–38 μg g⁻¹) in muscle fillets were found to be negatively correlated with total body weight (Fig. 1). Apparent decreasing concentrations in these two metal levels in muscle sample with increasing body weight were possibly due to factor such as dilution with growth. Growth may dilute metal concentrations in an organism if tissue is added faster than metal. Livers and gonads contained greater levels of the four metals than somatic muscle. Liver metal concentrations of Zn (range 29–108 μg g⁻¹) and Cd (range 0.06–0.37 μg g⁻¹) increased with total body weight. All equations fit data at P < 0.01 (Fig. 2). Positive correlations between size and metal concentrations suggest that net uptake may occur. Inessential, slowly exchanging metals such as Cd appear to reflect an uptake which tend to become a cumulative process (age dependence of concentrations). The occurrence of insignificant correlation between liver concentrations of Cu (mean value: 4 μg g⁻¹) and environmental concentrations of this metal was consistent with equilibration. Since fish are known to possess the metal binding protein metallothionein, a sequestering agent, detoxification of these metals in fish liver may be by sequestration rather than elimination. Increasing metal concentrations in liver may represent storage of sequestered products in that organ. In the gonads, no significant relationship exists between total body weight and trace metal contents. Results of t-test indicated that females had significantly greater Cu and Zn concentrations, but no significant difference existed between males and females for Cd concentrations (Figs 3 and 4). Thus, the relation between concentration and total body weight appears to be specific as to the species, tissues analyzed and environmental conditions. The comparison of metal concentrations in fish to assess variations in contamination levels requires understanding the relationship between metal concentration and body size within each population.     

Biomonitoring of trace metals in the Black Sea (Romania) using mussels Mytilus galloprovincialis

In a preliminary biomonitoring study, accumulated trace metal concentrations (Cd, Cu, Zn, Hg, Fe, Mn) have been measured in the mussel Mytilus galloprovincialis collected in the Black Sea, at 100 km from the Danube Delta in February 2001 and February 2002. Mussels were collected from four sites. In 2001 metal concentrations were determined in the whole soft body whereas, in 2002, the distribution of metals was evaluated in three different organs (gills, visceral mass and remaining tissues). The results obtained in 2002 confirmed those of 2001. For a given site, concentrations were always higher in the gills and visceral mass of mussels than in the remaining tissues. Principal component analysis allowed separating stations as a function of the metal concentrations in the organs. It is concluded that the mussels M. galloprovincialis are suitable biomonitors to assess changes in metal pollution in this coastal area of the Black Sea.     

Concentrations of cadmium, lead and zinc in livestock feed and organs around a metal production centre in eastern Kazakhstan

This paper presents results of analysis of animal feed and meat (cattle, horse and sheep) products from a metal processing region (Oskemen) in east Kazakhstan. Samples were collected from a range of districts of differing distances from the main source of anthropogenic pollution and with differing underlying metal-containing geologies. Analyses for cadmium, lead and zinc revealed high concentrations in many feed and meat samples. Horse (an important food animal) samples had higher levels of contamination than cattle, which were higher than sheep. For example, mean cadmium concentrations in horse kidneys in one district were found to be 128 mg/kg and lead concentrations for liver 2.2 mg/kg. These, and other, results are generally higher than reported in many other studies in contaminated regions of eastern Europe and they can exceed State Maximal Allowed Concentrations by many times. As such levels of contamination pose a significant potential risk to human health, these results have formed the basis for subsequent research on levels of metal contamination in human tissues from affected populations.     

Detection of localized methylmercury contamination by use of the mussel adductor muscle in Minamata Bay and Kagoshima Bay, Japan

Based on our previous finding that the concentrations of total mercury in mussel adductor muscle approximated those of methylmercury, we compared concentrations of total mercury in the adductor muscle of the mussel Mytilus galloprovincialis, collected from four sites around Minamata City from 1993 to 1995 and four sites in Kagoshima Bay from 1997 to 1998, to assess the level of localized methylmercury contamination. Though the input of mercury from the chemical plant had stopped by around 1970, concentrations of total mercury in the mussel adductor muscle were higher at two sites (26-121 ng/g, n = 135) near the main fallout of wastewater from the chemical plant in Minamata Bay than at the other sites, i.e. two sites 1-5 km from the former sites in Minamata City (6-28 ng/g, n = 52), and all sites in Kagoshima Bay (2-30 ng/g, n = 287). The localized methylmercury contamination around the chemical plant in Minamata Bay was documented also by our sensitive analysis of mercury concentrations in seawater and sediment samples. The survey of concentrations of total mercury in the mussel adductor muscle seems to be useful for monitoring the methylmercury contamination in coastal areas.     

Lead in the tissues of terrestrial raptors in southern Ontario, Canada, 1995-2001

Terrestrial raptors which feed on upland hunted game species may increase their risk to lead exposure and lead poisoning by ingesting lead shot found in the tissues of prey. Lead exposure in 225 individuals of nineteen species of terrestrial raptors, collected as carcasses in southern Ontario from 1995-2001, was examined through the analysis of bone, liver and kidney tissues. In this study, one red-tailed hawk contained liver lead concentrations and exhibited signs consistent with lead poisoning. Liver and kidney concentrations of one turkey vulture were also significantly higher than that associated with subclinical effects. This same bird, plus another turkey vulture and a northern harrier, had elevated bone lead concentrations (>10 microg/g dw) associated with possible toxicity. Turkey vultures had the highest mean concentrations of lead in bone and kidney compared to other raptor species. While it appeared only a single bird suffered acute lead poisoning, lead levels exceeded threshold concentrations associated with subclinical or acute toxicity in 4 of 225, almost 2%, of terrestrial raptors assessed. Given the association between lead exposure in raptors and hunting of game species reported in other studies, the continued use of lead shot for upland hunting in Ontario likely remains as one of the primary sources of lead and a continued risk to these birds of prey.     

Concentrations of selected essential and non-essential elements in arctic fox (Alopex lagopus) and wolverines (Gulo gulo) from the Canadian Arctic

Arctic fox (Alopex lagopus) and wolverine (Gulo gulo) tissues were collected in the Canadian Arctic from 1998 to 2001 and analyzed for various essential and non-essential elements. Several elements (Ag, Al, As, B, Ba, Be, Co, Cr, Mo, Ni, Sb, Sn, Sr, Tl, U and V) were near or below the detection limits in >95% arctic fox and wolverine samples. Concentrations of Cd, Cu, Fe, total Hg (THg), Mn, Pb, Se and Zn were quantifiable in >50% of the samples analyzed and reported herein. Hepatic elemental concentrations were not significantly different among arctic foxes collected at Ulukhaqtuuq (Holman), NT (n=13) and Arviat, NU (n=50), but were significantly greater than concentrations found in wolverine liver from Kugluktuk (Coppermine), NU (n=12). The mean (+/-1 S.E.) concentrations of Cd in kidney were also significantly greater in arctic fox (1.08+/-0.19 microg g(-1) wet wt.) than wolverine (0.67+/-0.18 microg g(-1) wet wt.). However, mean hepatic Cu concentrations (Ulukhaqtuuq: 5.5+/-0.64; Arviat: 7.1+/-0.49 microg g(-1) wet wt.) in arctic foxes were significantly lower than in wolverines (32+/-3.3 microg g(-1) wet wt.). Hepatic total Hg (THg) concentrations in arctic fox from this study were not significantly different from specimens collected in 1973, suggesting that THg concentrations have not changed dramatically over the past 30 years. The mono-methylmercury (MeHg) concentrations in selected (n=10) arctic fox liver samples from Arviat (0.14+/-0.07 microg g(-1) wet wt.) comprised 14% of THg. While the molar concentrations of THg were correlated with Se in arctic foxes and wolverines, the hepatic Hg/Se molar ratios were consistently lower than unity; suggesting that Se-mediated detoxification pathways of Hg are not overwhelmed at current exposure.     

Trace metal concentrations in water,sediments and fish tissue from Lake Tanganyika

Trace metal (Cu, Pb, Fe, Mn, Zn, Cd) concentrations were determined in water, sediments, various fin fish species and a bivalve (Mutela spekei) from Lake Tanganyika using an atomic absorption spectrophotometer. Integrated water samples to depths of 10 m were collected using a pre-rinsed flexible plastic pipe. Sediment samples were collected using a ponar mud sampler. Fish samples were obtained using a variety of fishing techniques. No differences in trace metal concentrations were observed in both inshore and offshore waters. Levels in inshore sediments were much higher than for the offshore ones. Sediment input through run-off may have been the cause for the differences. However, the levels were much lower than those reported for Lake Malawi sediments. The concentrations in the fish tissue were within ranges reported elsewhere for Lake Tanganyika fish species. The centrapomid Lates stappersii and the clupeids Limnothrissa miodon and Stolothrissa tanganicae are the most important commercial species in the lake followed by Lates marie. Lead and cadmium are of concern to human health. The mean concentrations of the two metals in the commercial fish species were as follows: L. stappersii (5.03 microg Pb/g, 0.28 microg Cd/g); L. marie (4.96 microg Pb/g, 0.25 microg Cd/g); L. miodon (4.64 microg Pb, 0.38 microg Cd); and S. tanganicae (4.96 microg Pb/g, 0.39 microg Cd/g). Levels of lead and iron in the bivalve species were exceptionally very high, being 11.08 and 6.54 mg/g, respectively.     

Levels of non-essential elements in muscle from harp seal (Phagophilus groenlandicus) and hooded seal (Cystophora cristata) caught in the Greenland Sea area

The non-essential elements, arsenic, cadmium, mercury and lead, inevitably accumulate in marine top predators such as seals. The concentration of these elements and the essential element selenium, due to its proposed protective properties against mercury toxicity in marine mammals, were measured in muscle, liver and kidney from reproductive active females of harp seal (Phagophilus groenlandicus) and hooded seal (Cystophora cristata) caught in the drift ice between Iceland and East Greenland. Arsenic levels were below 1 microg/g w.w. in all analysed samples, and were therefore low compared to other seafood products. The concentrations of arsenic found in the present study were comparable to the results reported in a similar study from 1985. Mean concentrations of total mercury in muscle from the present study were higher than levels in other seafood products. The levels of total mercury from the present study showed a tendency of lower levels in all tissue samples compared to the study from 1985. Methyl mercury displayed a trend of a lower ratio of methyl mercury to total mercury as the concentration of total mercury increased, indicating a demethylation of methyl mercury at high total mercury concentrations (e.g. mercury in liver of hooded seal). The concentration ratio of methyl mercury to total mercury in muscle samples was more than 75%, with total mercury concentration less than 0.5 microg/g w.w., whereas the ratio for liver was as low as 0.2% with a total mercury concentration of 128 microg/g w.w. The molar concentration ratios of selenium to mercury showed that selenium was present in a molar surplus to mercury in all tissues with low mercury concentration. However, there seemed to be a general mobilisation of selenium in liver and kidney tissues of harp seal and hooded seal, whereas an extraordinary mobilisation seemed to take place at hepatic mercury concentrations exceeding 50 microg/g w.w. The mean concentrations of lead in muscles in the present study were higher than in fish and other seafood products from the Barents Sea. The lead concentrations from the present study were lower than levels reported in the 1985 study. However, the levels of the non-essential elements analysed in muscle from the two seal species in the present study should not prevent the use of seal meat in human nutrition.     

Determination of anthropogenic input of Ru, Rh, Pd, Re, Os, Ir and Pt in soils along Austrian motorways by isotope dilution ICP-MS

A joint study with the Federal Environment Agency of Austria was carried out to determine the distribution of Ru, Rh, Pd, Os, Ir and Pt (PGE) and Re in soils along major motorways. Emphasis was put on Ir as to date little is known about its anthropogenic input as this metal is now also used in automobile catalytic converters. Soil samples were analysed by ICP-MS through online-coupling of a chromatographic column to separate the PGEs from interfering matrix constituents. At all sampled sites not only Rh, Pd and Pt but also Ir and Re significantly exceed natural background values; concentrations reached 13 ng/g, 25 ng/g, 134 ng/g, 1.1 ng/g and 9.8 ng/g, respectively. The analytical procedure proved to be very selective and sensitive and, therefore applicable to routine soil analysis.     

Organic pollutants in wild ducks from New York state: I. Interspecies differences in concentrations and congener profiles of PCBs and PCDDs/PCDFs

Wild ducks of three species, common mergansers (Mergus merganser americanus), gadwalls (Anas streptera), and mallards (Anas platyrhynchos), were collected near industrial sites in the Massena, NY area of the St. Lawrence River (SLR) in 1988/89 and 1994. Additional samples were collected in 1994 near a former polychlorinated biphenyl (PCB) capacitor plant at Fort Edward, NY (a mallard and two wood ducks (Aix sponsa)), and at control sites (common mergansers, mallards and wood ducks). On a lipid basis, PCB concentrations in liver tissue from the 1994 collection ranged from 0.1 mug/g in a control wood duck to 676 mug/g in a common merganser from the SLR area. However, the highest total polychlorinated dibenzofuran (PCDF) concentrations were found in liver and fat tissues of gadwalls and mallards collected near the SLR industrial sites (2.8-12 ng/g lipid). These two species bioaccumulated non-2,3,7,8-substituted PCDFs in addition to 2,3,7,8-PCDF isomers, whereas common mergansers preferentially bioaccumulated 2,3,7,8-substituted PCDFs. The mergansers from the SLR sites were the only specimens contaminated with polychlorinated dibenzo-p-dioxins (PCDDs), which were all 2,3,7,8-substituted. The PCB and PCDF congener patterns in the duck tissues appear to have been influenced by both sampling location and species trophic level.     

Loggerhead sea turtle (Caretta caretta) egg yolk concentrations of persistent organic pollutants and lipid increase during the last stage of embryonic development

Data are scarce describing the concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides in sea turtle eggs. The purpose of this study was to establish appropriate sample collection methodology to monitor these contaminants in sea turtle eggs. Contaminant concentrations were measured in yolk samples from eggs that failed to hatch from three loggerhead sea turtle (Caretta caretta) nests collected in southern Florida to determine if concentrations change through embryonic development. One to three egg yolk samples per nest were analyzed from early, middle, and late developmental stages (n=22 eggs total). PCB and pesticide concentrations were determined by gas chromatography with electron capture detection (GC-ECD). Geometric mean concentrations of summation operatorPCBs (52 congeners), summation operatorDDTs, summation operatorchlordanes, and dieldrin in all eggs were 65.0 (range=7.11 to 3930 ng/g lipid), 67.1 (range=7.88 to 1340 ng/g lipid), 37.0 (range=4.04 to 685 ng/g lipid), and 11.1 ng/g lipid (range=1.69 to 44.0 ng/g lipid), respectively. Early and middle developmental stage samples had similar concentrations of PCBs and organochlorine pesticides on a wet-mass basis (ng/g tissue extracted), but the concentrations doubled by the late stage. This increase is most likely attributable to the 50% increase in lipid content observed in the late-stage yolk. These findings indicate that an early-stage sample cannot be directly compared to a late-stage sample, especially from different nests. These preliminary findings also allowed us to calculate the minimum number of eggs per nest required for analysis to obtain an acceptable mean concentration per nest. More research is required to investigate geographical trends of contaminant concentrations and potential health effects (i.e., abnormalities) caused by these contaminants on sea turtle development.     

Evidence for the transfer of polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans from soil into biota

The concentrations of six indicator and co-planar polychlorinated biphenyls (PCBs), 17 polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDD/Fs) were determined in soil and associated biota samples collected from a polluted and wasted farmland in southern China. The sum of six indicator PCBs (Nos 28, 52, 101, 138, 153 and 180) concentrations in biota samples were proportional to the total amount of PCBs that transferred from soil to the corresponding biota samples, and the sum six indicator PCB congeners in samples were about 20% of the total PCBs, respectively. The ratios of the sum six indicator PCBs and the total PCBs in samples collected in the same area were approximately equal. The sums of six indicator PCBs were proportional to the total PCBs that transferred from soil to plant, while the co-planar PCBs were not. Analysis of individual PCB and PCDD/F congener signatures in soil revealed the original pollutant source after transportation and biodegradation for 14 years using principal component analysis (PCA). The pattern of PCBs in soils and plants could reflect the original pollution source after transportation and biodegradation for 14 years, while the pattern of PCBs in the terrestrial animals could not reflect the primary source. The consumption foods in this region such as foraging chicken eggs, foraging duck eggs, and loach (Misgurnus anguillicaudatus) were highly contaminated, the total toxicity equivalent (TEQ) was up to 784 pg WHO-TEQ/g on basis lipid in foraging chicken eggs.     

Enhanced methods for assessment of the trace element composition of Iron Age bone

Modern, ultra-trace, analytical methods, coupled with magnetic sector ICP-MS (HR-ICP-MS), were applied to the determination of a large suite of major and trace elements in Iron Age bones. The high sensitivity and un-paralleled signal-to-noise characteristics of HR-ICP-MS enabled the accurate measurement of Ag, Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cu, Fe, La, Li, Mg, Mn, Ni, P, Pb, Pt, Rb, Sr, U, V, and Zn in small bone sections (<75 mg). Critically, the HR-ICP-MS effectively addressed molecular interferences, which would likely have compromised data generated with quadrupole-based ICP-MS instruments. Contamination and diagenetic alteration of ancient bone are grave concerns, which if not properly addressed, may result in serious misinterpretation of data from bone archives. Analytical procedures and several chemical and statistical methods (Principal Components Analysis - PCA) were studied to assess their utility in identifying and correcting bone contamination and diagenetic alteration. Uncertainties in bone (femur) sampling were characterized for each element and longitudinal variation was found to be the dominant source of sampling variability. However the longitudinal variation in most trace elements levels was relatively modest, ranging between 9 and 17% RSD. Bone surface contamination was evaluated using sequential acid leaching. Calcium-normalized metal levels in brief, timed, dilute nitric acid leaches were compared with similarly normalized interior core metal levels to assess the degree of surface enrichment. A select group of metals (Mn, Co, Ni, Ag, Cd, and Pt) were observed to be enriched by up to a factor of 10 in the bone surface, indicating that that these elements may have a higher contamination component. However, the results of sequential acid leaching experiments indicated that the single acid leaching step was effective in removing most surface-enriched contaminants. While the leaching protocol was effective in removing contaminants associated with the bone surface, there remained potentially significant residual levels of soil-sourced contaminant tracers within the leached bone. To address this issue a mathematical procedure, based on metal/aluminum ratios, was developed to correct-for the soil-contaminant metal pools. Soil correction fractions for the primary anthropogenically mobilized metals evaluated were greatest for Pb (13.6%) followed by As (4.4%), Ag (3.9%), and Cd (0.94%). Although median soil corrections were typically low, many samples did require a much larger correction, thus both bone cleaning and soil corrections may be necessary to realize accurate endogenous bone elemental data. The results of the PCA analysis were remarkably consistent with outcomes from the chemical and elemental ratio protocols evaluated in the study, and suggest that loadings on certain factors will be helpful in screening for soil-biased samples and in identifying diagenetically altered bone. Application of these contamination evaluation and correction tools was made possible by the high-quality, multi-element, datasets produced by HR-ICP-MS. Large variations in bone core concentrations between the 80 Iron Age specimens examined were observed for all the primary trace elements and in many of the supporting elements, even after correction for major contaminant components.