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Since 1987, the World Health Organization (WHO) carried out global surveys on polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in human milk. This study presents a review of the three most recent surveys from 2000 to 2010, including DDT. The objective was to identify global quantitative differences and provide baseline information for 52 countries or provide time-trends for countries with previous data. Individual human milk samples were collected following a WHO-designed procedure and combined to form a national pooled sample. Here, we report global levels for PCDDs, PCDFs, PCBs and the sum of o,p′-DDT, p,p′-DDT, o,p′-DDE, p,p′-DDE, o,p′-DDD and p,p′-DDD (ΣDDTs). A concise risk–benefit evaluation related to human milk contamination with these persistent organic pollutants (POPs) was also done. Large global and regional differences were observed. Levels of PCDDs and PCDFs were highest in India and some European and African countries. PCB levels were highest in East and West Europe. The highest levels of ΣDDTs were found in less industrialized countries. A temporal downward trend for PCDDs, PCDFs and PCBs is indicated. A risk–benefit assessment indicates that human milk levels of PCDDs, PCDFs and PCBs are still significantly above those considered toxicologically safe, while ΣDDTs are below or around those considered safe. With respect to potential adverse health effects, a more dominant role of in utero exposure versus lactational exposure is indicated. If potential adverse effects are balanced against positive health aspects for (breastfed) infants, the advantages of breastfeeding far outweigh the possible disadvantages. Our observations provide a strong argument to plea for further global source-directed measures to reduce human exposure further to dioxin-like compounds.

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The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30-or 60-m-length, 0.25 mm inner diameter (id), and 25 μm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r 2 > 0.998) for calibration curves ranging from 100 fg/μL to 1000 pg/μL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is much easier to use.

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One-dimensional nuclear magnetic resonance (NMR) Is a valuable tool for structural elucidation of perfluorinated materials. The value of ieF 1-D NMR diminishes, however, In multicomponent systems due to rapidly Increasing spectral complexity. The alternative of separatlon/purtflcatlon of these complex liquid mixtures can be prohibitively costly and time consuming. Physical-chemical property similarities potentially prohibit component purification using standard chromatographic techniques. The application of two-dimensional 19F NMR techniques to complex perfluorinated liquid mixtures has provided previously unobtainable Information about the number and structure of components. The Impact of homonuclear Hartmann Hahn (HOHAHA) and homonuclear relayed coherence transfer (COSYRCT) on component Identification In Isomer mixtures was explored. With component Identification and subsequent 1-D 19F spectral assignments completed, quantitation via routine methods could be performed. The ability to extract one-dlmenslonal 19F spectra of "pure" Individual components from both the 2-D HOHAHA and COSYRCT experimental spectra and their unique advantages, disadvantages, and limitations as tools for spectroscopic separation of complex liquid mixtures were demonstrated.

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