Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.

Process and outcome evaluation of the hepatitis B perinatal vaccination program in Houston, Texas, 1991--1993

A retrospective cohort study was designed to evaluate the compliance of vaccination dose schedules and vaccination effectiveness at 12 months of age among a total of 226 high-risk infants born to HBsAg-positive pregnant women who participated in the HBV Perinatal Vaccination Program in Houston, Texas, 1991-1993.^ The seroprevalence of HBsAg-positivity was 0.5% among pregnant women who attended prenatal clinics in Houston, Texas, 1991-1993. The Asian women had the highest seroprevalence rate (5.9%), followed by black (1.9%), white (0.7%), and Hispanic women (0.3%). The seroprevalence of HBsAg increased with age (p =.02); the highest seroprevalence rate found among the $>$40 group (5.4%), followed by the 20-40 age group, and the $<$20 age. A steady increase was observed in the number of infants, from 45 in 1991, to 103 in 1993. The majority of these infants were black (58.0%), followed by Hispanic (28.8%), Asian (8.4%), and white infants (4.0%). Significant increases were observed from 1991 to 1993 in the number of infants who initiated vaccination (86.7% to 98.1%, p =.02) and in those infants who were post-tested at 12 months of age (24.4% to 44.7%, p =.04). During the same period an increase was also observed in the number of infants who completed the vaccination dose schedules (62.2% to 72.8%, p =.37). The compliance rates were not statistically significant regarding gender, race or ethnicity, health service area, medical referral source, and residential geographic areas. About 56.0% of the reasons cited for non-compliance among the 144 infants who neither completed the vaccination dose schedules nor received the 12-month post-test were "moved," and "no response/not at home." A total of 82 infants completed the vaccination dose schedules and were post-tested at 12 months of age for anti-HBs-positivity, and 96.3% of these infants seroconverted. A race-specific statistically significant seroconversion difference was found among infants who received all vaccination doses and were post-tested at 12 months of age (100% for the black and the white, 96.3% for the Hispanic, and 80.0% for the Asians infants, p =.05).^ From a public health perspective, the HBV Perinatal Vaccination Program improved during its first three years (1991-1993). It was effective in preventing perinatal HBV infection in almost 97.0% of infants who were vaccinated and post-tested. To increase the efficiency and efficacy of the program, the following recommendations are proposed: (1) Increase the vaccination compliance rate by educating and improving the tracking, communication and coordination channels with those individuals involved in the process and by increasing staff resources. (2) Reduce the post-test vaccination non-compliance by post-testing infants simultaneously with third vaccination dose at 6 months of age, and only post-test those infants who are anti-HBs-negative at 9-12 months of age. (Abstract shortened by UMI.) ^

Concentrations of natural and anthropogenic organohalogens in water and air samples in the Canadian Arctic during IPY (2007-2008)

Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg/L) were as follows: alpha-hexachlorocyclohexane (alpha-HCH) 465-1013, gamma-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg/m**3) were as follows: alpha-HCH 7.5-48, gamma-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4-39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of alpha-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The alpha-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic alpha-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng/m**2/d) were as follows: alpha-HCH 6.8 ± 3.2 (2.7-13), gamma-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng/m**2/d (-1.6 to 2.0).

Chemistry of hot waters sampled from basaltic basement at DSDP Hole 83-504B

Seawater that has been altered by reaction with basaltic basement has been sampled from Deep Sea Drilling Project Hole 504B, located on 5.9-m.y.-old crust on the southern flank of the Costa Rica Rift. Fourteen water samples have been collected on Legs 69, 70, and 83, both before and after renewed drilling on the latter two legs, at temperatures from 69 to 133°C and pressures from 390 to 425 bars. The water sampled prior to renewed drilling on Leg 83 had occupied the hole for nearly 2 yr. since it was last flushed with surface seawater at the end of Leg 70. Despite some contamination by seawater during sampling, the composition of two of these waters has been determined by using nitrate as a tag for the contaminant. Both the 80 and 115°C waters have seawater chlorinity, but have lost considerable Mg, Na, K, sulfate, and 02, and have gained Ca, alkalinity, Si, NH3 and H2S. The loss of sulfate is due to anhydrite precipitation, as indicated by the d34S value of the remaining dissolved sulfate. The 87Sr/86Sr ratio has been lowered to 0.7086 for the 80°C water and 0.7078 for the 115°C water, whereas the Sr concentration is nearly unchanged. The changes in major element composition relative to seawater are also larger for the 115°C water, indicating that the basement formation water at this site probably varies in composition with depth. Based on their direction relative to seawater, the compositional changes for the 80 and 115°C waters do not complement the changes inferred for the altered rocks from Hole 504B, suggesting that the bulk composition of the altered rocks, like their mineralogy, is largely unrelated to the present thermal and alteration regime in the hole. The exact nature of the reacted seawaters cannot be determined yet, however. During its 2 yr. residence in the hole, the surface seawater remaining at the end of Leg 70 would have reacted with the wall rocks and exchanged with their interstitial formation waters by diffusion and possibly convection. How far these processes have proceeded is not yet certain, although calculations suggest that diffusion alone could have largely exchanged the surface seawater for interstitial water. The d18O of the samples is indistinguishable from seawater, however, and the d14C of the 80°C sample is similar to that of ocean bottom water. Although the interpretation of these species is ambiguous, that of tritium should not be. Tritium analyses, which are in progress, should clarify the nature of the reacted seawaters obtained from the hole.