We present a new analytical method, which allows the simultaneous analysis of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I) in geological samples. To account for interferences of Fe on the spectral lines of F, of Al on Br-lines, and of Ca on I-lines, we prepared four new halogen-free calibration glasses. The new method is used to analyze various glass reference materials and crystal-hosted melt inclusions from the Azores. Our results show that our new method allows reliable and reproducible analyses of all four halogens in silicate glasses.

Chlorine is the most abundant halogen in sedimentary formation waters with concentrations from <100 to >250000 mg/l. Bromine is the second most abundant halogen at <1 mg/l to >6000 mg/l with iodine from <0.1 mg/l to >100 mg/l and fluorine from <0.1 mg/l to 30 mg/l. Chlorine and bromine show a strong systematic covariation suggesting that they are subject to the same controlling mechanisms. Fluorine only shows relatively high concentrations at elevated chlorine and bromine concentrations showing that fluorine, chlorine and bromine are possibly controlled by the same processes. Iodine does not correlate with any of the other halogens indicating that unique processes control iodine.

Key geological parameters that influence chlorine and bromine (and possibly fluorine) concentrations are the presence of salt in a basin, the age of the reservoir unit and the kerogen-type within the main hydrocarbon source rock in a basin. The presence of salt in a basin shows that sea water was evaporated to halite saturation producing connate waters with high concentrations of chlorine and bromine. The presence of salt also leads to high salinity waters through water-salt interaction during burial and diagenesis. Tertiary reservoirs typically have much lower chlorine and bromine concentrations than Mesozoic or Palaeozoic reservoirs. The age of the reservoir unit may simply reflect the different amounts of time available for formation water to interact with salt. The dominance of type II marine kerogen in a basin leads to higher bromine concentrations. This may reflect the dominance of a marine influence in a basin which is more likely to lead to salt deposition than terrestrial depositional environments. Iodine concentrations are independent of all these parameters. Other geological parameters such as depth of burial, temperature, basin forming mechanism and reservoir lithology have no influence upon halogen concentrations.

Key processes that affect halogen concentrations are sea water evaporation and dilution, water—salt interaction and input from organic sources. Chlorine and bromine data lie close to the experimentally-derived sea water evaporation trend showing that sea water evaporation may be an important general control on halogens. Sea water dilution is probably responsible for most low salinity formation water chlorine and bromine concentrations for the same reason. Sea water dilution can occur either by meteoric invasion during burial, or following uplift and erosion, or by diagenetic dehydration reactions. Water can interact with salt in a variety of ways: halite dissolution by congruent processes, halite recrystallization by incongruent processes, sylvite dissolution or recrystallization and halite fluid inclusion rupture. Halite dissolution will lead to high chlorine and relatively low bromine waters because halite contains little bromine. In contrast, halite recrystallization will lead to bromine-enhanced waters because NaBr dissolves preferentially to NaCl. The occurrence of dissolution or recrystallization will depend on the water rock ratio, greater volumes of water will lead to more dissolution and waters with higher Cl/Br ratios. Sylvite is usually rich in bromine so dissolution will lead to bromine-enhanced waters. Primary aqueous inclusions in halite contain high bromine concentrations so that rupture, during deformation or recrystallization, will lead to bromine-enhanced formation water. A combination of these processes are responsible for the very limited range of Cl/Br ratios although congruent halite dissolution must have a limited role due to the absence of waters with high Cl/Br ratios.

Iodine is strongly concentrated in organic materials in the marine environment; oils and organic rich-source rocks have high I/Cl and I/Br ratios relative to sea water or evaporated sea water. All formation waters are enriched in iodine relative to sea water implying that there has been input from organic matter or interaction with oil. However, hydrocarbon source rock type in a basin has no discernible effect upon iodine concentrations.

Microprobe analyses of the halogen contents of apatites from two samples of amphibolite-facies schist from Connemara, Ireland, have been used to calculate the fugacity ratios fHCl/fH2O and fHF/fH2O using the experimental data of Korzhinskiy. The results imply fugacities for both acids in the range 0.03 to 0.1 bars, but whereas for the lower grade rock fHF > fHCl, the migmatitic sample gives fHF⋍fHCl. An independent estimate of fHF/fH2O from the biotite composition in one sample is in acceptable agreement with the result obtained from apatite.

Coexisting scapolite, biotite and hornblende in scapolite-biotite rocks from the Tongmugou Pb-Zn deposit, Qinling, northwestern China are characterized by high levels of chlorine. Scapolite composition varies from EqAn27 to EqAn47 with 47–80 wt.% Cl. The scapolite composition is a sensitive indicator of the NaCl activity in coexisting hydrothermal fluid. Biotite contains 0.3–1.2 wt. % Cl and also has high F contents (0.2–0.7 wt.%). The hornblende is a Cl-rich hastingsite with Cl>3.5 wt.% and high (Na2O + K2O) contents (3.2–3.9 wt. %), high Xk [= K/(K + Na)] values (0.45–0.55) and high XFc [= Fe/(Fe + Mg)] values (0.76–0.79). The chlorine within these minerals is thought to be derived from evolved seawater. The scapolite-biotite rocks are products of Cl-rich alteration of volcanoclastic sedimentary rocks during submarine hydrothermal processes. Multiple-stage hydrothermal activity culminated with the circulation of a high-NaCl fluid that was also responsible for the formation of the massive sulphide deposits.

We have performed an initial assessment of the feasibility of producing heavy negative ion beams as drivers for an inertial confinement fusion reactor. Negative ion beams offer the potentially important advantages relative to positive ions that they will not draw electrons from surfaces and the target chamber plasma during acceleration, compression, and focusing, and they will not have a low energy tail. Intense negative ion beams could also be efficiently converted to atomically neutral beams by photodetachment prior to entering the target chamber. Depending on the target chamber pressure, this atomic beam will undergo ionization as it crosses the chamber, but at chamber pressures at least as high as 1.3 × 10−4 torr, there may still be significant improvements in the beam spot size on the target, due to the reduction in path-averaged self-field perveance. The halogens, with their large electron affinities, are the best negative ion candidates. Fluorine and chlorine are the easiest halogens to use for near-term source experiments, whereas bromine and iodine best meet present expectations of driver mass. With regard to ion sources and photodetachment neutralizers, this approach should be feasible with existing technology. Except for the target chamber, the vacuum requirements for accelerating and transporting high energy negative ions are essentially the same as for positive ions.

The ore-element associations of granite-related ore deposits in the eastern Australian Palaeozoic fold belts can be related to the inferred relative oxidation state, halogen content and degree of fractional crystallisation within the associated granite suites. Sn mineralisation is associated with both S- and I-type granites that are reduced and have undergone fractional crystallisation. Cu and Au are associated with magnetite- and/or sphene-bearing, oxidised, intermediate I-type suites. Mo is associated with similar granites that are more fractionated and oxidised. W is associated with a variety of granite types and shows little dependence on inferred magma redox state. The observed ore deposit-granite type distribution in eastern Australia, and the behaviour of ore elements during fractionation, is consistent with models of ore element sequestering by sulphides and Fe-Ti phases (e.g. pyrrhotite, ilmenite, sphene, magnetite) whose stability is nominally fO2-dependent. Fractional crystallisation acts to amplify this process through the progressive removal of compatible elements and the concentration of incompatible elements into decreasing melt volumes. The halogen content is also important. S-type granites are poorer in Cl than I-types. Cl decreases and F increases in both S- and I-type granites with fractional crystallisation. Low Cl contents combined with low magma fO2 in themselves seem to provide an adequate explanation for the rarity of Mo, Cu, Pb and Zn type mineralisation with S-type granites. Although such properties of granite suites seem adequately to predict the associated ore-element assemblage to be expected in associated mineral deposits, additional factors determine whether or not there is associated economic mineralisation.