In reviewing the distribution of fluorine in igneous rocks it is clear that F abundance is related to alkalinity and to some extent to volatile contents. Two important F-bearing series are recognized: (1) the alkali basalt—ultrapotassic rocks in which F increases with increasing K2O and decreasing SiO2 contents; and (2) the alkali basalt—phonolite—rhyolite series with F showing positive correlation with both total alkalis and SiO2. Detailed studies of series (1) show that F abundance in ultrapotassic magmas (lamproite, kamafugite, lamprophyre) occurs in descending order in the sequence phlogopite>apatite>amphibole>glass. Fluorine contents in the same minerals from fresh and altered mantle xenoliths may be several orders of magnitude less than those in the host kamafugite. For many lamproites, F contents correlate with higher mg# suggesting that F is highest in the more primitive magmas.

Experiments at mantle conditions (20 kbar, 900–1400°C) on simplified F-bearing mineral systems containing phlogopite, apatite, K-richterite, and melt show that F is generally a compatible element. Additionally, low F abundance in minerals from mantle xenoliths suggests that F may not be available in mantle source regions and hence is unlikely to partition into the melt phase on partial melting. Melting experiments on the compositions of F-free and F-bearing model phlogopite harzburgite indicate that even small variations in F content produce melts similar in composition to those of lamproite.

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.

The concentrations of Br in potable groundwaters in the United Kingdom range from 60 to 340 µg 1-1. The occurrence of Br is described in terms of the Br/Cl weight ratio which enables small changes in bromide concentrations to be assessed in terms of salinity. Median values of Br/Cl in groundwaters range from 2.60 to 5.15 × 10−3 compared with a sea water ratio of 3.47× 10−3. In recent shallow groundwaters the Br/Cl ratio is rather variable in response to a range of natural and anthropogenic inputs (marine and industrial aerosols, industrial and agricultural chemicals including road salt). Some slight enrichment in Br/Cl also occurs naturally during infiltration as a result of biogeochemical processes.

Evolution of Br/Cl along groundwater flow lines reflects the sources of increasing salinity; either the influence of marine sedimentary formations or evaporites. The groundwaters in the Triassic sandstones of the English Midlands show significant Br depletion due to the evaporite source, in contrast to groundwaters in Cumbria. Br/Cl ratios in the Sherwood Sandstone of the East Midlands mainly reflect the natural input sources and can be used to help understand the palaeohydrology.

Magnetite—apatite deposits associated with the Atacama Fault Zone of northern Chile are interpreted here, on field criteria, as being the products either of hydrothermal fluids with a strong magmatic signature, or of late-stage Fe-rich magmas mixed with an aqueous fluid. Even in the Chilean iron belt, apatite-rich magnetite deposits are a rarity. Variations in F- and Cl- contents in apatites, strongly zoned with respect to halogens, are indicative of primary variations in fHF and fHCI in the hydrothermal fluids. Small variations in halogen fugacities in the aqueous fluid are capable of buffering large variations in halogen content within apatite crystals in equilibrium with that fluid. The recorded halogen zonation profiles are inconsistent with crystallization of the apatites simply from a volatile-rich, late-stage fractionation Fe-rich magma, or its derived magmatic vapour. It is more likely that they are the result of mineral—fluid buffering with a fluid that represents the mixing of a magmatically-derived aqueous fluid with a meteoric fluid that has variably scavenged Ca and Cl from within the country rocks. The source magma of the former is probably an Fe-P enriched acidic magma, derived by fractionation of primary calc-alkaline basic magmas.

Pyrrhotites in polished sections from more than twenty stratabound massive sulphide and magmatic nickel-copper deposits in Norway were studied under the microscope using the magnetic colloid method. In both types of deposits, two distinct styles of intergrowths between monoclinic and hexagonal pyrrhotites were found: crystallographically-controlled lamellar intergrowths and fissure-controlled irregular intergrowths.

Lamellar intergrowths consist of crystallographically oriented monoclinic lamellae occurring in a hexagonal matrix and were produced originally by exsolution from hexagonal pyrrhotite on cooling. Irregular intergrowths comprise blades and patches of monoclinic pyrrhotite occurring along fissures and grain boundaries of hexagonal pyrrhotite, and were formed by interactions between hexagonal grains and sulphur-rich hydrothermal solutions.

Increase in lamella thickness and spacing, development of lamella zonations, wedge-shaped composite ends, boxworks and composite lamellae were caused by progressive lamellae coarsening and maturation during natural annealing, which could have been promoted by anisotropic stress. Metamorphic recrystallization and annealing tend to homogenize pyrrhotite and erase preexisting exsolution lamellae.

Bismuthinite-bearing quartz veins from the Alston Block of the North Pennine Orefield are all close to, or above, the Rookhope and Tynehead cupolas of the buried Weardale Granite. They are uniform in composition and paragenesis and are earlier than the main fluorite-baryte-galena-sphalerite mineralization of the orefield. Rhythmical crystallization of quartz, chalcopyrite and minor pyrite is followed by fluorite-quartz-chalcopyrite-minor sphalerite-altered pyrrhotite mineralization. Early tin-bearing (up to 0.29 wt.% Sn) chalcopyrite encloses trace amounts of bismuthinite (Bi2S3), synchysite (CaREE(CO3)F2), argentopentlandite (Ag(FeNi)8S8) (close to being stoichiometric), pyrrhotite, cubanite and cosalite (Pb2Bi2S5), while early pyrite carries monoclinic pyrrhotite (close to Fe7S8) and tungsten-bearing cassiterite (up to 1.03 wt.% WO3). Bismuthinite is macroscopically visible and is associated with native bismuth and small, fine-grained, spherical aggregates that qualitative analysis suggests may be cosalite crystals. Synchysite and more rarely monazite, xenotime and adularia are intergrown with bismuthinite. These mineralogical data form part of the basis for an increasing awareness of the contribution of the Weardale Granite to the early phases of mineralization in the Alston Block.

The Afon Goch (Anglesey, UK) is a short (12 km source to estuary) stream highly contaminated by acid mine drainage (AMD) throughout its length, due to past-mining at the head of the stream. Metal distribution is strongly controlled by the pH, which increases downstream particularly at confluences with two unpolluted tributaries. A pH increase causes precipitation of metals, primarily Fe as hydroxide, thus altering the transport of the metal load, potentially allowing storage of metal within the river as deposited material. However, further work suggests that the controls on whether metal can behave non-conservatively, and therefore the controls on metal distribution, are more complicated than being purely pH dependent. This is because much of the Fe load, even at the low pH at the head of the stream, is not soluble Fe3+ but colloidal Fe hydroxide. Consequently, coagulation is a requisite intermediate step between precipitation and potential for settling. It is possible that in reaches of the stream away from tributary confluences, the process of coagulation is the predominant influence on metal distribution. Furthermore, because much of the metal load in the water column is very fine, its deposition results in a sediment in which the metals can be intimately associated with a biofilm at the sediment/water interface. Such associations change both deposition and erosion characteristics of the sediment and have implications for subsequent diagenesis and mineral morphology.

Radial and longitudinal temperature gradients within cold-seal pressure vessels can contribute significantly to the total temperature unccrtainty in any one experiment and it is important to calibrate such gradients before experiments are undertaken. We have measured temperature gradients in vertically mounted large cold-seal vessels at 1 atm and 1 kbar and in the temperature range 500–800°C Radial gradients were measured with the vessel at various positions within the furnace by recording the temperature difference between a thermocouple in the internal bore of the vessel and one in a well in the top of the vessel. We find that when the vessel is at a certain position in the furnace, the temperatures read by these two thermocouples are equivalent to within 1°C. The contribution of radial gradients to temperature uncertainty can be thus be substantially minimized if experiments are undertaken with the vessel in this position. Longitudinal gradients of 2.8°C/cm at 500°C and 3°C/cm at 800°C were recorded at 1 kbar. These profiles are significantly steeper than those recorded at 1 atm. Not to calibrate temperature gradients at the experimental conditions or failure to calibrate vessels at all could lead to large temperature uncertainties.

Armalcolite and pseudobrookite have been crystallized from synthetic melts of basaltic composition with variable amounts of added TiO2. It was found that the composition of the armalcolite and pseudobrookite are dependent on the TiO2 content of the melt and the conditions (particularly oxygen fugacity, but also temperature and quenching rate) of formation. The maximum Al2O3 content of pseudobrookite appears to be ∼14–15 wt.% Al2O3, a spinel-like phase being exsolved at higher Al2O3 concentrations. Generally armalcolite is formed at low pO2 and pseudobrookite at higher oxygen fugacities.

Three natural spinels of different places of occurrence and compositions were investigated by means of microprobe chemical analysis, single crystal X-ray diffraction and Mössbauer spectroscopy. All cation distributions between T and M sites were calculated from microprobe and XRD experimental data, by means of a mathematical model with appropriate assumptions. Fe2+ and Fe3+ assignments calculated in this way were compared with those observed in Mössbauer spectra. The satisfactory agreement found proves, at least in the samples studied, the reliability of the model and the assumptions used. In the spinels examined, such results show Fe2+ and Fe3+ virtually ordered in T and M sites respectively. Mössbauer data also revealed Fe2+ in different tetrahedral sites due to the next-nearest neighbour effect, probably as a consequence of spinel genetic conditions.

Noélbensonite, a new mineral, is the barium manganese analogue of lawsonite. It is described from the Woods ornamental rhodonite mine, 30 km NNE of Tamworth, New South Wales, Australia, where it occurs as aggregates of blocky to sometimes lamellar crystals ranging from a few micrometres to (rarely) 100 µm in length. It replaces NaMn amphibole, namansilite, and pectolite, and also occurs as tiny monomineralic veinlets 0.05–0.25 mm thick. Rare euhedral crystals are dominated by {100} and {011}, with (011) ^ = 68°. The mineral is orthorhombic, space group apparently Cmcm; a = 6.325(1), b = 9.120(1), c = 13.618(1) Å, V = 785.6(1) Å3, with a : b : c = 0.694 : 1 : 1.493. Noélbensonite is brittle, fracture irregular, Mohs hardness about 4, cleavage and twinning not observed, colour dark brown, streak paler yellow-brown, lustre earthy on some veinlet surfaces to brilliantly vitreous, calculated density 3.87 g/cm3, refractive indices α = 1.82(1),β (calculated from 2V) = 1.835(10), γ = 1.85(1), biaxial negative 2Vα = 46°(3°), strong dispersion r > v, straight extinction to plane of flattening, {100}, α ∥ c, β ∥ b, γ ∥ a with pleochroism in very thin sections: α = orange yellow, β = orange, γ = brownish orange, absorption γ > β ⇐p; α. The average of 23 electron microprobe analyses (wt.%) is SiO2 26.02, Al2O3 0.17, TiO2 0.01, Fe2O3 0.19, Mn2O3 34.76, CaO 0.31, Na2O 0.14, BaO 29.08, SrO 1.51, H2Ocalc 7.87, total 100.06, leading to the simplified formula . Up to 15% Sr and 9% Ca substitute for Ba in the large-cation sites. The strongest lines in the X-ray powder diffraction pattern are [(Iobs) dobs/Å hkl] (100) 4.85 111; (50) 4.557 020; (59) 4.322 021; (77) 3.416 113,004; (80) 2.869 202; (47) 2.849 114; (82) 2.729 024; (45) 2.543 132; (48) 2.428 222; (38) 2.255 223,041. The name is for William Noél Benson (1885–1957), in honour of his classic researches in the New England Fold Belt and of his tenure of the Chair of Geology at the University of Otago.

Danalite is the Fe2+ end-member of the minerals of the helvite group, which have the general formula M8(BeSiO4)6S2, with M = (Mn,Fe2+,Zn). These minerals are relatively uncommon, although limited amounts are known at many localities round the world (e.g. Ragu, 1994; Larsen, 1988; Kwak and Jackson, 1986, and references therein). Their typical host rocks are skams, but occurrences in mineralized veins pegmatites, and altered alkali granites have also been reported. Danalite is rarer than helvite (Mn endmember) and genthelvite (Zn end-member) and, unlike the other two end-members, has never been found nor synthesized as a pure mineral (Mel'nikov et al., 1968).

The Mg—Fe orthoamphibole series □ (Mg, Fe)7Si8O22(OH)2 — Na(Mg, Fe)5- Al2Si5Al3O22(OH)2 has an open end in the sense that the Si5 end member has not been found in nature; tiny domains of near end–member composition in intricately zoned crystals (Schumacher, 1980; Robinson et al. 1982), appeared to be intergrowths of two different double-chain silicates (Schumacher, pers. comm., 1994).

The 100 Ma complex LCT-type composite pegmatite- aplite dykes, intruded into various units of the Southern California Batholith, are known to contain bismuth minerals. Jahns and Wright (1951) reported the following primary and secondary bismuth minerals from the quartz-rich cores of a number of dykes in the Pala district, San Diego Co., California: native bismuth, bismuthinite, bismite, bismutite, and beyerite.