Polychlorinated biphenyl compounds in milk and dairy products

Summary The PCB content of 469 milk and dairy product samples was determined. The fat was extracted and cleaned up through aluminium oxide. The organochlorine pesticides and the PCBs were separated by chromatography through a silica gel column. The PCBs in the purified extracts were perchlorinated to decachlorobiphenyl and determined by gas chromatography. The mean PCB content of the samples investigated was 0.18 mg per kg fat. The results are comparable with those obtained in neighbouring countries and significantly lower than the interim FDA tolerance of 1.5 mg per kg fat.

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Polychlorierte Biphenylverbindungen in Milch und Milcherzeugnissen

Zusammenfassung Der Gehalt an polychlorierten Biphenylverbindungen wurde in 469 Milch- und Milcherzeugnis-Proben bestimmt. Das Fett wurde extrahiert und über Aluminiumoxid gereinigt. Die Organochlorpesticide und die PCB's wurden durch Chromatographie über eine Silicagelkolonne getrennt. Die PCB's der gereinigten Extrakte wurden zu Dekachlorbiphenyl perchloriert und durch Gaschromatographie bestimmt. Der durchschnittliche PCB-Gehalt der gesamten Muster betrug 0,18 mg pro kg Fett. Die Ergebnisse können mit denen der Nachbarländer verglichen werden und sind bedeutsam niedriger als die vorläufige FDA-Toleranz von 1,5 mg pro kg Fett.

     

Relative congener scaling of Polychlorinated dibenzo-p-dioxins and dibenzofurans to estimate building fire contributions in air, surface wipes, and dust samples

The United States Environmental Protection Agency collected ambient air samples in lower Manhattan for about 9 months following the September 11, 2001 World Trade Center (WTC) attacks. Measurements were made of a host of airborne contaminants including volatile organic compounds, polycyclic aromatic hydrocarbons, asbestos, lead, and other contaminants of concern. The present study focuses on the broad class of polychlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) with specific emphasis on the 17 CDD/CDF congeners that exhibit mammalian toxicity. This work is a statistical study comparing the internal patterns of CDD/CDFs using data from an unambiguous fire event (WTC) and other data sets to help identify their sources. A subset of 29 samples all taken between September 16 and October 31, 2001 were treated as a basis set known to be heavily impacted by the WTC building fire source. A second basis set was created using data from Los Angeles and Oakland, CA as published by the California Air Resources Board (CARB) and treated as the archetypical background pattern for CDD/CDFs. The CARB data had a congener profile appearing similar to background air samples from different locations in America and around the world and in different matrices, such as background soils. Such disparate data would normally be interpreted with a qualitative pattern recognition based on congener bar graphs or other forms of factor or cluster analysis that group similar samples together graphically. The procedure developed here employs aspects of those statistical methods to develop a single continuous output variable per sample. Specifically, a form of variance structure-based cluster analysis is used to group congeners within samples to reduce collinearity in the basis sets, new variables are created based on these groups, and multivariate regression is applied to the reduced variable set to determine a predictive equation. This equation predicts a value for an output variable, OPT: the predicted value of OPT is near zero (0.00) for a background congener profile and near one (1.00) forthe profile characterized by the WTC air profile. Although this empirical method is calibrated with relatively small sets of airborne samples, it is shown to be generalizable to other WTC, fire source, and background air samples as well as other sample matrices including soils, window films and other dust wipes, and bulk dusts. However, given the limited data set examined, the method does not allow further discrimination between the WTC data and the other fire sources. This type of analysis is demonstrated to be useful for complex trace-level data sets with limited data and some below-detection entries.     

Levels and congener distributions of PCDDs, PCDFs and Co-PCBs in Japanese retail fresh and frozen vegetables

To evaluate dioxin contamination in retail vegetables, congener analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) were performed on sixty varieties of fresh vegetables including cereals and mushrooms, obtained from Japanese supermarkets in 2002. The toxic equivalent quantity (TEQ) levels for dioxins in samples ranged from < 0.001 to 0.089 pg-TEQ/g wet weight, when undetected and trace were taken as zero. Among the samples, dioxins were generally detected in green leafy vegetables. The highest TEQ value was for mulukhiya (0.089 pg-TEQ/g), followed by spinach and komatsuna (Japanese mustard spinach) (0.077 and 0.074 pg-TEQ/g, respectively). Additionally, the dioxin levels in seventeen varieties of frozen vegetables were also determined, and showed TEQ values ranging from < 0.001 to 0.080 pg-TEQ/g. The total TEQ in commercial vegetables mainly reflected the levels of 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3',4,4',5-PeCB (#126) (the sum of them represented 63% of the total TEQ).     

Contamination levels and congener distributions of PCDDs, PCDFs and Co-PCBs in several fast foods in Japan

We determined the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) in three types of fast foods [(1) seventeen hamburgers and two hot dogs, (2) six portions of fried potatoes and (3) three chicken products] obtained from fast food shops or convenience stores in Japan. All samples tested showed low toxic equivalent quantity (TEQ) levels of dioxins in the range of 0.001-0.083 pg-TEQ/g wet weight (0.006-0.053 pg-TEQ/g for hamburgers and hot dogs, 0.001-0.083 pg-TEQ/g for fried potatoes and 0.053-0.065 pg-TEQ/g for chicken products). The congener profile in hamburgers and hot dogs suggested that the total TEQ was mainly determined by Co-PCBs, especially by 3,3',4,4',5-PeCB (#126), which accounted for 44% of the total TEQ value. Findings for animal foods such as beef and cheese were consistent with this result. For fried potatoes, PCDD/Fs accounted for 94% of the total TEQ value, and 2,3,4,7,8-PeCDF accounted for 32% of PCDD/Fs. Dioxins in the chicken products consisted of 3,3',4,4',5-PeCB (#126) and 1,2,3,7,8-PeCDD, which accounted for 23% and 21% of the total TEQ, respectively. If an adult (50 kg weight) eats 150 g of hamburger, 100 g of potatoes and 150 g of chicken, the daily intake is estimated to be 0.299 pg-TEQ/kg b.w./day using the average values (0.022, 0.028 and 0.059 pg-TEQ/g, respectively) obtained in this study. This value corresponds to 7.5% of the tolerable daily intake (TDI) for PCDD/Fs and Co-PCBs in Japan.     

Videomicroscopic comparison of bull sperm and leukocyte chromosome areas as related to gender

Chromosomal areas from metaphase spreads of male bovine leukocytes were digitized and sex chromosomes identified using videomicroscopy. Autosomal areas were ranked in descending order within a cell and assigned to two categories based on alternating rank. X and Y chromosome areas were assigned to respective categories. Areas were divided by 4 to make their sum equivalent to sperm DNA content. Data were analyzed before and after inclusion of sex chromosomal areas. Before X and Y inclusion, rank contributed to difference in chromosomal areas. Rank by category interaction and category effects did not contribute to area variation. After X and Y inclusion, area variation was due to rank by category interaction, rank, and category. Differences between sums of chromosomal areas across categories was 3.57%. Head areas of morphologically normal sperm with intact acrosomes were digitized using the same optics as chromosomal areas. Sum of corrected chromosomal areas per category was used in discriminant analysis to assign sperm head areas to two categories with .5 prior probabilities. Assignment resulted in 1037 sperm in one category and 1177 in the other. Difference between largest sperm head area classes across categories was 3.2%. Discrimination of sperm head areas, based on sum of chromosomal area and measured with computerized videomicroscopy, may be used to evaluate sex of bovine spermatozoa.     

Polychlorinated biphenyl residues in food and human milk: determination of co-planar and mono-ortho substituted congeners

An analytical method is described for determining the residues of coplanar as well as mono-ortho substituted PCB congeners both exhibiting toxicological relevance, in foods of animal origin and in human milk. The unsophisticated procedure, convenient for routine analyses, includes the extraction of lipids, clean-up steps using liquid/liquid partition and column chromatography, fractionation of the congeners using HPLC on a special carbon column with an optimal gradient elution, and capillary column gas chromatography with electron capture or mass spectrometric detection. As preliminary results indicate, the low-chlorinated PCB technical products contribute more to the actual contamination of environment and foods than has been estimated so far. Obviously the co-planar congeners are accumulated during the food chain in a portion different from that found for the other congeners.     

Polychlorinated biphenyl concentrations in adult chinook salmon (Oncorhynchus tshawytscha) returning to coastal and Puget Sound hatcheries of Washington State

Identifying the source of polychlorinated biphenyls (PCBs) is the first step to eliminating contamination within anadromous salmonids and other aquatic species. We evaluated PCB concentrations in the muscle tissue of 4-year old Puget Sound and coastal hatchery Chinook salmon in an effortto identify potential locations where contamination occurs. Ten muscle samples were taken from each of two Puget Sound hatcheries and two coastal hatcheries in Washington State to determine PCB concentrations. Two technical mixtures of PCBs, Aroclor 1254 and Aroclor 1260, were measured in the tissue samples collected. Aroclor 1254 was detected in all samples, while Aroclor 1260 was detected in 16 of 40 samples. Generalized linear modeling (GLM) was used to evaluate the influence of region (Puget Sound and coast), hatchery, sex, fish length, and percent lipids on PCB concentrations. Twenty different GLMs representing multiple null hypotheses were ranked using Akaike Information Criterion (AIC). Six of the 20 models evaluated had substantial support for being the best model to describe PCB concentrations in Chinook salmon. The six models with substantial support were region and lipids; region; hatchery and lipid; region and sex; region, sex, and lipids; and region and length. Region appears to be the most influential variable explaining the variation in PCB concentrations in Chinook salmon in the Pacific Northwest. PCB concentrations in Chinook salmon muscle tissue from Puget Sound hatcheries were significantly greater (mean 49.26 microg/kg wet weight and standard deviation 40.55 microg/kg) than those from coastal hatcheries (mean 17.41 microg/kg wet weight and standard deviation 6.8 microg/kg). Our results suggest that some contamination likely occurs in the Pacific Ocean. However, a larger source likely exists within Puget Sound or along the migratory route of Puget Sound Chinook salmon. The observation of PCBs in Chinook salmon also has important implications for human health and salmon carcass supplementation.     

Polychlorinated biphenyl residues in the golden grey mullet (Liza aurata) from Tunis Bay,Mediterranean sea (Tunisia)

Concentrations of polychlorinated biphenyls (PCBs) were determinated in the muscle tissues of mullets (Liza aurata) caught from two coastal marine areas in Tunis bay, “Raoued” and “Radès”. Twenty congeners were detected in all the fish samples analyzed, among which were 4 congeners recommended by the European Union for assessing pollution and 4 “dioxin-like” congeners. Residue levels of total PCBs ranged from 45 to 194 ng/g wet wt in the mullet from “Radès” and from 43 to 65 ng/g w wt in specimens from “Raoued”. Hexachlorobiphenyls were predominant in fishes caught from both “Raoued” and “Radès” areas, accounting for 43% and 40%, respectively. The individual PCB profiles were dominated by congeners 153 in mullet from “Raoued” and PCB 200 in fishes from “Radès”. The levels of TEQs of “dioxin-like” congeners were 3.4 pg/g w wt for fishes from “Raoued” and 2.5 pg/g w wt for specimens from “Radès”.     

Dairy wastewater, aquaculture, and spawning fish as sources of steroid hormones in the aquatic environment

A suite of androgens, estrogens, and progestins were measured in samples from dairy farms, aquaculture facilities, and surface waters with actively spawning fish using gas chromatography-tandem mass spectrometry (GC/MS/ MS) to assess the potential importance of these sources of steroid hormones to surface waters. In a dairywaste lagoon, the endogenous estrogens 17beta-estradiol and estrone and the androgens testosterone and androstenedione were detected at concentrations as high as 650 ng/L. Samples from nearby groundwater monitoring wells demonstrated removal of steroid hormones in the subsurface. Samples from nearby surface waters and tile drains likely impacted by animal wastes demonstrated the sporadic presence of the steroids 17beta-estradiol, estrone, testosterone, and medroxyprogesterone, usually at concentrations near or below 1 ng/L. The endogenous steroids estrone,testosterone, and androstenedione were detected in the raceways and effluents of three fish hatcheries at concentrations near 1 ng/L. Similar concentrations were detected in a river containing spawning adult Chinook salmon. These results indicate that dairy wastewater, aquaculture effluents, and even spawning fish can lead to detectable concentrations of steroid hormones in surface waters and that the concentrations of these compounds exhibit considerable temporal and spatial variation.     

Assessment of the variation of skin barrier function with anatomic site,age, gender and ethnicity

The skin is the largest organ of the human body and its functions include protection, thermoregulation sensation and secretion. Significant advances in our understanding of how the morphology and physiology of the skin contribute to the skin’s barrier role have been achieved in recent years. The aim of this review is to summarize the principal approaches which have been used to assess variation in skin barrier function with anatomic site, age, gender, and ethnicity. The methods discussed include trans‐epidermal water loss (TEWL) measurement, assessment of corneocyte size, response to vasoactive compounds and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) interrogation of skin. The utility of the various methods is considered and the most important findings in the literature to date are highlighted.     

Differential accumulation of polychlorinated biphenyl congeners in the terrestrial food web of the Kalamazoo River Superfund site, Michigan

A series of field studies was conducted to determine the bioaccumulation of polychlorinated biphenyl (PCB) congeners in the terrestrial food web of the Kalamazoo River flood plain. Samples included colocated soils, native plants likely to be consumed by wildlife, several taxa of terrestrial invertebrates, small mammals, passerine bird eggs, nestlings, and adults, and great horned owl plasma and eggs. Mean concentrations of total PCBs in samples from the former Trowbridge impoundment were 6.5 mg/kg dry weight for soils and 0.023, 0.13, 1.3, 1.3, 1.6, and 8.2 mg/kg wet weight for plants, small herbivorous mammals, depurated earthworms, shrews, great horned owl eggs, and house wren eggs, respectively. Historical data from the Kalamazoo River have reported Aroclor-equivalent total PCB concentrations in the terrestrial food web; however, the degree of environmental weathering of the parent PCB mixtures was unknown. In this study, earthworms and composite samples of coleoptera exhibited PCB congener patterns that were similar to patterns in colocated soils. However, in plants, less chlorinated PCBs (e.g., mono-, di-, tri-, and tetrachlorinated biphenyls) were predominant, and in small mammals, there was a notable enrichment of PCBs 153, 180, 138, 118, and 99. In general, concentrations of PCBs were lower in most biota than in soil from the Kalamazoo River Area of Concern (KRAOC) although there was a modest biomagnification of PCBs from lower trophic level biota to highertrophic levels. As a consequence of environmental weathering of PCBs in the terrestrial food web of the KRAOC, the relative potency of the PCBs (expressed as mg TEQs/kg PCBs) decreased from soil to most biota. While there was a general trend, as expected, in which concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) increased with total PCBs, this relationship was rather poor (R2 = 0.13). Taken together, these data suggest that the differential accumulation of PCB congeners in the terrestrial food web can be explained by congener-specific differences in bioavailability from soil, exposure pathways, and metabolic potential of each of the food web components.     

Differential accumulation of polychlorinated biphenyl congeners in the aquatic food web at the Kalamazoo River Superfund site, Michigan

A series of field studies were conducted to gain a better understanding of the bioaccumulation and dynamics of polychlorinated biphenyl (PCB) congeners in the aquatic food web of the Kalamazoo River flood plain. Representative species of passerine birds, mammals, fish, aquatic plants, invertebrates, and colocated sediments were collected from areas located within submerged portions of the former Trowbridge impoundment and also from areas located at an upstream reference location. In most matrixes, total concentrations of PCBs were significantly greater in the downstream study area compared to the upstream reference location. Patterns of PCB congeners varied among trophic levels due to selective bioaccumulation of more chlorinated congeners in upper trophic level organisms. There were no statistically significant differences in total PCB concentrations among sampling grids within either site or temporally among three sampling seasons between May and September. The greatest total PCB concentrations were detected in adult tree swallows (mean = 8.7 mg/kg wet weight (ww)) and fish (mean = 4.4 mg/ kg ww) collected from the former Trowbridge impoundment. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) were greatest in egg, nestling, and adult tree swallows collected from the former Trowbridge impoundment. There was not a significant correlation between concentrations of total PCBs and TEQs at either site in the mammalian or avian food webs. The relative potency of the mixture of PCBs, expressed as the ratio of TEQs to total PCBs, increased with trophic position in the avian and mammalian aquatic food webs located within the former Trowbridge impoundment.     

Partitioning, desorption, and dechlorination of a PCB congener in sediment slurry supernatants

Partitioning and desorption played specific roles in the dechlorination of 2-chlorobiphenyl (2-CIBP) in sediment slurry supernatants, which are suspensions of dissolved organic matter (DOM). In short-term experiments, the partition coefficient (Kp) was related to the apparent dechlorination rate constant. The Kp value (160 L g(DOC)(-1)), which is independent of the DOM concentration, was determined based on the decrease of the apparent rate constant with the increase of the DOM concentration. In the long-term experiments, the overall rate of dechlorination can be described with a two-compartment model. The time constant for the sediment compartment was related to Kp and the desorption rate constant (k(d)). The k(d) value (0.21 h(-1)) was determined based on the decrease of the time constant values with an increasing DOM concentration. The use of DOM suspensions allowed a short time for equilibrium. Separation of the aqueous and DOM phases was not needed due to the dechlorination of 2-CIBP. The fundamental relationships between overall dechlorination rate constant and properties of the contaminant and sediment were established.     

Perchlorate uptake in spinach as related to perchlorate, nitrate, and chloride concentrations in irrigation water

Several studies have reported on the detection of perchlorate (ClO(4)(-)) in edible leafy vegetables irrigated with Colorado River water. However, there is no information on spinach as related to ClO(4)(-) in irrigation water nor on the effect of other anions on ClO(4)(-) uptake. A greenhouse ClO(4)(-) uptake experiment using spinach was conducted to investigate the impact of presence of chloride (Cl(-)) and nitrate (NO(3)(-)) on ClO(4)(-) uptake under controlled conditions. We examined three concentrations of ClO(4)(-), 40, 220, and 400 nmol(c)/L (nanomoles of charge per liter of solution), three concentrations of Cl(-), 2.5, 13.75, and 25 mmol(c)/L, and NO(3)(-) at 2, 11, and 20 mmol(c)/L. The results revealed that ClO(4)(-) was taken up the most when NO(3)(-) and Cl(-) were lowest in concentration in irrigation water. More ClO(4)(-) was detected in spinach leaves than that in the root tissue. Relative to lettuces, spinach accumulated more ClO(4)(-) in the plant tissue. Perchlorate was accumulated in spinach leaves more than reported for outer leaves of lettuce at 40 nmol(c)/L of ClO(4)(-) in irrigation water. The results also provided evidence that spinach selectively took up ClO(4)(-) relative to Cl(-). We developed a predictive model to describe the ClO(4)(-) concentration in spinach as related to the Cl(-), NO(3)(-), and ClO(4)(-) concentration in irrigation water.     

Influence of 4-week intraduodenal supplementation of quercetin on performance,glucose metabolism,and mRNA abundance of genes related to glucose metabolism and antioxidative status in dairy cows

Quercetin has been shown to be a potent antioxidant, acts hepatoprotectively, and affects glucose and lipid metabolism in monogastrics. If this is also true in ruminants, quercetin could be beneficial in periparturient high-yielding dairy cows by ameliorating the negative effects of free radical formation and reducing the severity of liver lipidosis and ketosis. In a first attempt to evaluate effects of a long-term quercetin treatment, we intraduodenally administered twice daily 18 mg of quercetin (Q)/kg of body weight to 5 late-lactation (215 d in milk) dairy cows over a period of 28 d. Frequent blood samples were taken before and during administration to determine plasma concentrations of flavonols and metabolites. Before and after 1 and 4 wk of Q administration, glycogen and fat content as well as mRNA expression of selected genes were measured in liver biopsies. Furthermore, euglycemic, hyperinsulinemic, and hyperglycemic clamp studies were conducted before and after 2 wk of Q administration. During the experiment, dry matter intake and most other zootechnical data remained unchanged. Milk protein content was increased in wk 2 and 4 of Q administration compared with basal values, whereas fat and lactose contents of milk remained unchanged. Plasma nonesterified fatty acids, γ-glutamyl transferase, cholesterol, glutamate dehydrogenase, triglyceride, and albumin concentrations, as well as liver fat and glycogen concentrations, were not affected by Q supplementation. Plasma glucose and β-hydroxybutyrate concentrations in plasma decreased and increased, respectively, under the influence of quercetin. During hyperglycemic clamp conditions, the relative increase of plasma insulin was higher after 2 wk of Q administration, and a tendency for an increased rQUICKI (revised quantitative insulin sensitivity check index) was observed. The relative mRNA expression levels of selected genes related to glucose metabolism, fat metabolism, and antioxidative status were not altered after 1 or 4 wk of Q supplementation. In conclusion, the effects on insulin release and sensitivity support the assumption that administration of Q could have positive effects on the metabolic adaption of high-yielding cows to early lactation. The increase of milk protein content in response to Q supplementation needs to be verified.     

Sex, BMI and age in addition to dietary intakes influence blood concentrations and congener profiles of dioxins and PCBs

Scope: The aim of this study was to i) characterize dietary polychlorinated biphenyls (PCBs) and dioxin exposure in consumers of fish from the PCB contaminated Lake Mjøsa in Norway ii) examine the influence of demographic factors on blood concentrations and congener composition of dioxins and PCBs, iii) characterize dietary sources and possible exposures above tolerable intake. Methods and results: Blood samples were analysed for dioxin‐like (dl) compounds (PCDD/Fs and dl‐PCBs) and non‐dl‐PCBs (ndl‐PCBs). Dietary exposures were calculated using food frequency questionnaires (n=64). Men had higher median intake of dl‐compounds than women (1.2 and 0.85 pg TEQ/kg bw/day), but similar blood concentrations (23.3 and 25.8, pg TEQ/g lipid weight (lw)). For non‐dl‐PCBs, intakes (6.5 and 4.5 ng/kg bw/day) and blood concentrations (381 and 224 ng/g lw) were higher in men than in women. Blood concentrations correlated with dietary intakes in men only. Increasing BMI and age elevated blood concentrations mainly in women. Men and women had different blood congener profiles, with a higher share of PCB‐126 in women, despite similar dietary congener profiles. Eleven participants exceeded the tolerable intake for dl‐compounds. Fish from Lake Mjøsa was the main dietary source. Conclusion: The higher influence of BMI and age for women than for men may have implications for risk assessment.     

Estimation of size-resolved ambient particle density based on the measurement of aerosol number, mass, and chemical size distributions in the winter in beijing

Simultaneous measurements of aerosol size, distribution of number, mass, and chemical compositions were conducted in the winter of 2007 in Beijing using a Twin Differential Mobility Particle Sizer and a Micro Orifice Uniform Deposit Impactor. Both material density and effective density of ambient particles were estimated to be 1.61 ± 0.13 g cm(-3) and 1.62 ± 0.38 g cm(-3) for PM(1.8) and 1.73 ± 0.14 g cm(-3) and 1.67 ± 0.37 g cm(-3) for PM(10). Effective density decreased in the nighttime, indicating the primary particles emission from coal burning influenced the density of ambient particles. Size-resolved material density and effective density showed that both values increased with diameter from about 1.5 g cm(-3) at the size of 0.1 μm to above 2.0 g cm(-3) in the coarse mode. Material density was significantly higher for particles between 0.56 and 1.8 μm during clean episodes. Dynamic Shape Factors varied within the range of 0.95-1.13 and decreased with particle size, indicating that coagulation and atmospheric aging processes may change the shape of particles.