Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Enantiomer ratios,patterns and levels of toxaphene congeners in human milk from Germany

High resolution gas chromatography (HRGC) coupled to quadrupole negative ion chemical ionization (NICI) mass spectrometry (MS) was used to investigate congener patterns, levels and enantiomer distribution of selected toxaphene congeners (#26, #41, #44, #50, #63, B7-1453) in human milk from Germany. #50 and #26 were the most abundant congeners. Furthermore, the identification of B7-1453, B8-1412, #41, #42, #44 and #63 was possible. Levels for the sum of #26, #41, #44 and #50 ranged from 7 to 24 microg kg(-1) milk fat and contributed between 2 and 9% to the total burden of investigated organochlorines such as selected compounds of the chlordane group, HCH, DDT and polychlorinated biphenyls (PCB). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Enantiomer ratios (ER) and enantiomer fractions (EF) of the abundant toxaphene congeners #26 and #50 as well as of B7-1453, #41 and #63 were determined. Greatest deviations from a racemic composition in individual human milk samples were found for #41 (1.54-2.37), #50 (1.37-1.72) and #63 (0.53-0.71) whereas ERs for #26 were close to 1. Compared to wildlife biota such as fish and raptors ER changes were more pronounced in human milk but comparable to human adipose tissue.     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Application of intrawell testing of RCRA groundwater monitoring data when no upgradient well exists

A statistical quality control approachto detect changes in groundwater quality from aregulated waste unit is described. The approachapplies the combined Shewhart-CUSUM control chartmethodology for intrawell comparison of analyteconcentrations over time and does not require anupgradient well. A case study from the U.S.Department of Energy's Hanford Site is used forillustration purposes. This method is broadlyapplicable in groundwater monitoring programs wherethere is no clearly defined upgradient location, thegroundwater flow rate is exceptionally slow, or wherea high degree of spatial variability exists inparameter concentrations. This study also indicatesthat the use of the Data Quality Objectives (DQO)process can assist in designing an efficient andcost-effective groundwater monitoring plan to achievethe optimum goal of both low false positive and lowfalse negative rates (high power).     

An Evaluation of Selenium Concentrations in Water, Sediment, Invertebrates, and Fish from the Republican River Basin: 1997–1999

The Republican River Basin of Colorado,Nebraska, and Kansas lies in a valley which contains PierreShale as part of its geological substrata. Selenium is anindigenous constituent in the shale and is readily leached intosurrounding groundwater. The Basin is heavily irrigated throughthe pumping of groundwater, some of which is selenium-contaminated, onto fields in agricultural production. Water,sediment, benthic invertebrates, and/or fish were collected from46 sites in the Basin and were analyzed for selenium to determinethe potential for food-chain bioaccumulation, dietary toxicity,and reproductive effects of selenium in biota. Resultingselenium concentrations were compared to published guidelines orbiological effects thresholds. Water from 38% of the sites (n = 18) contained selenium concentrations exceeding 5 g L^-1, which is reported to be a high hazard for selenium accumulation into the planktonic food chain. An additional 12 sites (26% of the sites) contained selenium in water between 3–5 g L^-1, constituting a moderate hazard. Selenium concentrations in sedimentindicated little to no hazard for selenium accumulation fromsediments into the benthic food chain. Ninety-five percent ofbenthic invertebrates collected exhibited selenium concentrationsexceeding 3 g g^-1, a level reported as potentially lethal to fish and birds that consume them. Seventy-five percent of fish collected in 1997, 90% in 1998, and 64% in 1999 exceeded 4 g g^-1selenium, indicating a high potential for toxicity andreproductive effects. However, examination of weight profilesof various species of collected individual fish suggestedsuccessful recruitment in spite of selenium concentrations thatexceeded published biological effects thresholds for health andreproductive success. This finding suggested that universalapplication of published guidelines for selenium may beinappropriate or at least may need refinement for systems similarto the Republican River Basin. Additional research is needed todetermine the true impact of selenium on fish and wildliferesources in the Basin.     

Luminescence spectroscopy as a screening tool for the potential carcinogenicity of asphalt fumes

A subset of polycyclic aromatic compounds (PACs), which contain 4-6 annulated rings, has been documented as the source of carcinogenicity in animal skin painting studies of petroleum products and asphalt fumes (M. L. Machado, P. W. Beatty, J. C. Fetzer, A. H. Glickman and E. L. McGinnis, Fundam. Appl. Toxicol., 1993, 21, 492; T. A. Roy, S. W. Johnson, G. R. Blackburn and C. R. Mackerer, Fundam. Appl. Toxicol., 1988, 10, 466). Because of the chemical complexity of these materials, it has been difficult to identify the specific compounds within this broad range of PACs responsible for their carcinogenicity. An alternative approach using luminescence spectroscopy was taken in this study to quantify, without identification, a subset of these compounds that appears to cause cancer. The fluorescence response at a specific wavelength pair was obtained for 39 laboratory asphalt fume condensates from animal skin painting studies, yielding a linear correlation coefficient of R2 = 0.96 between the fluorescence response in these materials and the carcinogenicity found in animal studies. In the absence of other asphalt fume condensates from animal studies, 17 petroleum oils were also evaluated using this method and compared with the available animal skin painting data. The details of the method include a clean-up step that removes the highly polar compounds and spectral subtraction of two- and three-ring PAC interference, both of which add to the fluorescence response, yet were not found to contribute to a carcinogenic response from skin painting studies. Full scan fluorescence plots also produce a fingerprint which can be used to assess contamination, such as coal tar products or mixtures of materials, that are not defined as asphalt, yet may be present in the working environment.     

Organic contaminants and trace metals in flounder liver and sediment from the Amsterdam and Rotterdam harbours and off the Dutch coast

Organic contaminants [polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), nonylphenols], organotin compounds and trace metals (cadmium, chromium, mercury and zinc) were determined in flounder (Platichthys flesus) liver and sediment from the Amsterdam harbour (North Sea Canal) and Rotterdam harbour (Euromonding) and off the Dutch coast between the Amsterdam and Rotterdam harbour mouths in order to assess the level of contamination in these harbours and to study contamination gradients.     

Effects of law enforcement and community outreach on mammal diversity in a biodiversity hotspot

Management activities such as law enforcement and community outreach are thought to affect conservation outcomes in protected areas, but their importance relative to intrinsic environmental characteristics of the parks and extrinsic human pressures surrounding the parks have not been explored. Furthermore, it is not clear which is more related to conservation outcomes—the management itself or local people's perceptions of the management. We measured objective (reports by park staff) and subjective (reports by local people) levels of community outreach and law enforcement based on responses to 374 questionnaires. We estimated mammal abundance and diversity of 6 protected areas based on data from 115 camera traps in Xishuangbanna, southwest China, a biodiversity hotspot with high hunting and land-conversion pressures. We then examined correlations among them and found that local people's perception of law enforcement was positively related to the local abundance of 2 large, hunted species, wild boar (Sus scrofa) (β = 15.22) and muntjac (Muntiacus vaginalis) (β = 14.82), but not related to the abundance of smaller mammals or to objective levels of enforcement. The subjective frequency of outreach by park staff to local communities (β = 3.42) and park size (β = 3.28) were significantly and positively related to mammal species richness, whereas elevation, human population density, and subjective frequency of law enforcement were not. We could not conclude that community outreach and law enforcement were directly causing increased mammal abundance and diversity. Nevertheless, the patterns we detected are some of the first empirical evidence consistent with the idea that biodiversity in protected areas may be more positively and strongly related to local perceptions of the intensity of park management than to either intrinsic (e.g., elevation, park size) or extrinsic (e.g., human population density) environmental factors.     

Genetic amniocentesis: 505 cases performed before the sixteenth week of gestation

Between May 1987 and November 1988, 505 early amniocentesis within the 15th week of gestation were performed at the First Department of Obstetrics and Gynaecology,‘L. Mangiagalli’ of the University of Milan and at the Department of Obstetrics and Gynaecology of ‘Gaslini’ hospital in Genoa. A total number often abnormal fetal karyotypes were diagnosed. In addition, one case of pseudomosaicism (not confirmed on fetal blood) and one case of osteogenesis imperfecta type II (observed at ultrasound examination) were also detected. Eleven pregnancies were therefore terminated because of an abnormal fetus. Out of 494 pregnancies (excluding terminated pregnancies) there were 16 fetal losses within the 28th week; ten of these occurred in the 2 weeks following the procedure. There were 475 live-births, of which 447 were term deliveries and the other 28 deliveries occurred before the 37th week of gestation.