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Understanding thefactors that control As concentrations in groundwater is vital for supplying safe groundwaterin regions with As-polluted aquifers. Despite much research, mainly addressing Holocene aquifers hosting young (12,000 yrs) groundwatersare not yet fully understood and so are assessed here through an evaluation of the redox properties of the system in a type locality, the PoPlain (Italy).Analyses of redox-sensitive species and major ions on 22 groundwater samples from the Pleistocene arsenic-affected aquifer in the Po Plain shows that groundwater concentrations of As are controlled by the simultaneous operation of several terminal electron accepters. Organic matter, present as peat, is abundant in the aquifer, allowing groundwater to reach a quasi-steady-state of highly reducing conditions close to thermodynamic equilibrium. In this system, simultaneous reduction of Fe-oxide and sulfate results in low concentrations of As (median 7 μg/L) whereas As reaches higher concentrations (median of 82 μg/L) during simultaneous methanogenesis and Fe-reduction. The position of well-screens is an additional controlling factor on groundwater As: short screens that overlap confining aquitards generate higher As concentrations than long screens placed away from them. A conceptual model for groundwater As, applicable worldwidein other Pleistocene aquifers with reducible Fe-oxides andabundant organic matter is proposed: As may have two concentration peaks, the first after prolonged Fe-oxide reduction and until sulfate reduction takes place, the second during simultaneous Fe-reduction and methanogenesis.

For several hundred years, farming in the Po Plain of Italy (46,000 km2, 20 million inhabitants) has been supported by intensive surface irrigation with lake and river water. Despite the longevity of irrigation, its effects on the quality and quantity of groundwater is poorly known and so is investigated here through seasonal measurements of hydraulic heads and water quality in groundwaters, rivers, lake, springs and rainwaters. In the north of the study region, an unconfined coarse-grained alluvial aquifer, infiltration of surface irrigation water, sourced from the Oglio River and low in NO3, contributes much to aquifer recharge (up to 88%, as evidenced by a δ2H-Cl/Br mixing model) and has positive effects on groundwater quality by diluting high concentrations of NO3 (decrease by 17% between June and September). This recharge also helps to maintain numerous local springs that form important local micro-environments. Any increase in water-use efficiency in irrigation will reduce this recharge, imperil the spring environments, and lessen the dilution of NO3 leading to increasing NO3 concentrations in groundwater. These findings can be extended by analogy to the entire Po Plain region and other surface-water-irrigated systems worldwide where inefficient irrigation methods are used and similar hydrogeological features occur.

in groundwaters from 145 wells across central West Bengal, India, those from Pleistocene aquifers at depths70 m beneath paleo-interfluves contain10 μg/L As. Pleistocene aquifers beneath deep paleo-channels typically host groundwaters containing 10-100 μg/L As at depths between 120 and 180 m. The depth profiles of As and SO4 and the conservative tracers Cl/Br, δ(18)O, and δ(2)H show that the As in Pleistocene groundwater beneath deep paleo-channels is relict and does not arise from migration downward of As-polluted groundwater in overlying aquifers. We postulate that the As was liberated in situ by reduction of minimal iron oxyhydroxides in the gray Pleistocene sands by organic matter infiltrating from riverbeds during late Pleistocene or earliest Holocene times. Mitigation of the widespread As-pollution in shallow aquifers through exploitation of deep Pleistocene aquifers would improve if guided by an understanding of the distribution of buried paleo-channels and paleo-interfluves and the knowledge that As may be present naturally in groundwater at depths150 m beneath deep paleo-channels.

Kolkata, the capital city of West Bengal, exploits groundwater for public water-supply. The groundwater has been reported to be widely polluted by arsenic (As). Analysis for As in 280 groundwaters from across Kolkata, failed to detect As concentrations >10 μg/L from natural processes. Arsenic concentrations between 10 and 79 μg/L found in 14 of the 280 groundwaters are remnant from a pollution-plume emanating from a single factory site where Paris Green, an arsenical pesticide, was manufactured between 1965 and 1985. In 45% of groundwaters sampled, concentrations of Mn exceed 0.4 mg/L, a putative health guideline value for drinking water. Sporadic minor hazards are posed by Pb > 10 μg/L introduced into groundwater from well-fittings, from 4% of groundwaters with F concentrations between 0.75 and 1 mg/L, and the 14% of groundwaters containing more than 500 mg/L Na, concentrations that might contribute to excessive daily intake of Na. Compounding hazards from As, F, Mn, Na, and Pb, shows that 64% of public wells and 40% of municipal wells supply groundwater of suspect quality. Groundwaters comply with WHO Guideline Values for drinking water in terms of Cr, Cu, Co, NO2, NO3, Sb, Se, and U. Aesthetic guideline values for Fe, Mn, SO4, and Cl are exceeded for many groundwaters.

In aquifers 160 to 260 m deep that used for public water-supply in an area ~ 150 km2 around the town of Cremona, in the Po Plain of Northern Italy, concentrations of arsenic (As) are increasing with time in some wells. The increase is due to drawdown of As-polluted groundwater (As ≤ 144 μg/L) from overlying aquifers at depths 65 to 150 m deep in response to large-scale abstraction for public supply. The increase in As threatens drinking-water quality locally, and by inference does so across the entire Po Plain, where natural As-pollution of groundwater (As > 10 μg/L) is a basin-wide problem. Using new and legacy data for Cl/Br, δ18O/δ2H and other hydrochemical parameters with groundwater from 32 wells, 9 surface waters, a sewage outfall and rainwater, we show that the deep aquifer (160–260 m below ground level), which is tapped widely for public water-supply, is partly recharged by seepage from overlying aquifers (65–150 m below ground level). Groundwater quality in deep aquifers appears free of anthropogenic influences and typically < 10 μg/L of As. In contrast, shallow groundwater and surface water in some, not all, areas are affected by anthropogenic contamination and natural As-pollution (As > 10 μg/L). Outfalls from sewage-treatment plants and black water from septic tanks firstly affect surface waters, which then locally infiltrate shallow aquifers under high channel-stages. Wastewater permeating shallow aquifers carries with it NO3 and SO4 which suppress reduction of iron oxyhydroxides in the aquifer sediments and so suppress the natural release of As to groundwater.

In forty six wells >150 m deep, from across the arsenic-polluted area of south-central Bangladesh, groundwater composition remained unchanged between 1998 and 2011. No evidence of deteriorating water quality was found in terms of arsenic, iron, manganese, boron, barium or salinity over this period of 13 years. These deep tubewells have achieved operating lives of more than 20 years with minimal institutional support. These findings confirm that tubewells tapping the deep aquifers in the Bengal Basin provide a safe, popular, and economic, means of arsenic mitigation and are likely to do so for decades to come. Nevertheless, concerns remain about the sustainability of a resource that could serve as a source of As-safe water to mitigate As-pollution in shallower aquifers in an area where tens of millions of people are exposed to dangerous levels of arsenic in well water. The conjunction of the stable composition in deep groundwater and the severe adverse health effects of arsenic in shallow groundwater lead us to challenge the notion that strong sustainability principles should be applied to the management of deep aquifer abstraction in Bangladesh is, the notion that the deep groundwater resource should be preserved for future generations by protecting it from adverse impacts, probably of a minor nature, that could occur after a long time and might not happen at all. Instead, we advocate an ethical approach to development of the deep aquifer, based on adaptive abstraction management, which allows possibly unsustainable exploitation now in order to alleviate crippling disease and death from arsenic today while also benefiting future generations by improving the health, education and economy of living children.

Across West Bengal and Bangladesh, concentrations of Cl in much groundwater exceed the natural, upper limit of 10 mg/L. The Cl/Br mass ratios in groundwaters range up to 2500 and scatter along mixing lines between waste-water and dilute groundwater, with many falling near the mean end-member value for waste-water of 1561 at 126 mg/L Cl. Values of Cl/Br exceed the seawater ratio of 288 in uncommon NO(3)-bearing groundwaters, and in those containing measurable amounts of salt-corrected SO(4) (SO(4) corrected for marine salt). The data show that shallow groundwater tapped by tube-wells in the Bengal Basin has been widely contaminated by waste-water derived from pit latrines, septic tanks, and other methods of sanitary disposal, although reducing conditions in the aquifers have removed most evidence of NO(3) additions from these sources, and much evidence of their additions of SO(4). In groundwaters from wells in palaeo-channel settings, end-member modelling shows that >25% of wells yield water that comprises ≥10% of waste-water. In palaeo-interfluvial settings, only wells at the margins of the palaeo-interfluvial sequence contain detectable waste water. Settings are identifiable by well-colour survey, owner information, water composition, and drilling. Values of Cl/Br and faecal coliform counts are both inversely related to concentrations of pollutant As in groundwater, suggesting that waste-water contributions to groundwater in the near-field of septic-tanks and pit-latrines (within 30 m) suppress the mechanism of As-pollution and lessen the prevalence and severity of As pollution. In the far-field of such sources, organic matter in waste-water may increase groundwater pollution by As.

Determination of the speciation of arsenic in groundwaters, using cathodic stripping voltammetry (CSV), is severely hampered by high levels of iron and manganese. Experiments showed that the interference is eliminated by addition of EDTA, making it possible to determine the arsenic speciation on-site by CSV. This work presents the CSV method to determine As(III) in high-iron or -manganese groundwaters in the field with only minor sample treatment. The method was field-tested in West-Bengal (India) on a series of groundwater samples. Total arsenic was subsequently determined after acidification to pH 1 by anodic stripping voltammetry (ASV). Comparative measurements by ICP-MS as reference method for total As, and by HPLC for its speciation, were used to corroborate the field data in stored samples. Most of the arsenic (78±0.02%) was found to occur as inorganic As(III) in the freshly collected waters, in accordance with previous studies. The data shows that the modified on-site CSV method for As(III) is a good measure of water contamination with As. The EDTA was also found to be effective in stabilising the arsenic speciation for longterm sample storage at room temperature. Without sample preservation, in water exposed to air and sunlight, the As(III) was found to become oxidised to As(V), and Fe(II) oxidised to Fe(III), removing the As(V) by adsorption on precipitating Fe(III)-hydroxides within a few hours.

We test the hypothesis that the noise in belemnite records through time results from changing climate. We do so by comparing palaeo-proxies (Mg/Ca, Sr/Ca, Na/Ca, δ18O, δ13C) in two species of Toarcian belemnites, Acrocoelites (Odontobelus) vulgaris (14 specimens) and Acrocoelites (Acrocoelites) subtenuis (10 specimens), deposited in a period of time that was short relative to the timescale of climate change. The specimens are interpreted to have been regurgitated from the stomach of a marine predator and so were deposited together in a geological instant of Early Jurassic time. In A. (O.) vulgaris, isotopic and elemental palaeo-proxies group tightly, suggesting that this belemnite occupied a restricted environmental niche. In A. (A.) subtenuis, elemental and isotopic compositions spread more widely, suggesting that this species occupied a greater range of habitats. Possible sexual dimorphism in A. (O.) vulgaris is reflected in bimodal Mg/Ca and differing intra-rostral distribution of Mg in putative dimorphs; concentrations decline by 30% from apical line to rim in specimens with high Mg/Ca, but are largely invariant radially in specimens with lower Mg/Ca. Sexual dimorphism in A. (A.) subtenuis yields a bimodality in size, Mg/Ca, and intra-rostral distribution of Mg; larger specimens have a higher Mg/Ca, and Mg concentrations that increase along radial traverses from apical line to rim, whilst the smaller specimens show a mid-rostral minimum in Mg concentration. Radial profiles of concentrations for Sr and Na vary little in all forms. Toarcian belemnites of these species thus show strong biofractionation effects on Mg/Ca, and little or no observable biofractionation of Sr/Ca or Na/Ca. It follows that much of the noise in belemnite records results from biofractionation, and from a cosmopolitan life-style of some belemnite species, rather than climate-change. For Toarcian belemnites, we suggest that Sr/Ca is the best indicator of palaeo-temperature.

In 49 samples of groundwater, sampled in Muzaffargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 μg L−1 in 58% of samples and reached up to 906 μg L−1. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 μg L−1. In fact, in rural areas, concentrations stay below 25 μg L−1 because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial or agricultural chemicals, or some other anthropogenic influence. Geochemical evidence suggests that pollutant organics from unconfined sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of which were found with >50 μg L−1 As. Here As concentrations seem to increase with depth and differing geochemical signatures are seen, suggesting that As concentrations in older groundwater may be governed by different processes. Other data on parameters of potential concern in drinking water are discussed briefly at the end of the paper.

In Bangladesh, concentrations of boron in groundwater reach 2.1 mg L −1 and are high regionally in alluvial aquifers of Late Pleistocene/Holocene age. Concentrations exceed 0.5 mg L −1 across approximately 6700 km 2 of the deep aquifer (>150 m depth) and 3000 km 2 of the shallow aquifer ( −1 and high values are widespread in the NE of the county. These concentrations exceed the regulatory guideline values for human consumption of 0.5 mg L −1 (WHO) or 0.9 mg L −1 (USA). The boron has desorbed from mineral surfaces as freshwater flushing displaces saline waters from the aquifers. In Bangladesh, desorption is driven by decreasing ionic strength, the equilibrium re-adjustment of mineral sorption sites to the low boron concentration in freshwater, and competitive exchange with HCO 3 /CO 3 . In deep Bangladesh aquifers in Barisal District (>250 m deep), boron enrichment delineates a buried estuary marking a previous course of the Ganges and/or Brahmaputra rivers. Boron enrichment is accompanied by ion-exchange that depletes Ca and enriches Na in the flushing freshwater. The patterns of enrichment and depletion indicate the direction of water quality change, in terms of salinization or freshening, with greater sensitivity than absolute chemical parameters.

In order to investigate the mechanism of As release to anoxic ground water in alluvial aquifers, the authors sampled ground waters from 3 piezometer nests, 79 shallow (80 m) wells, in an area 750 m by 450 m, just north of Barasat, near Kolkata (Calcutta), in southern West Bengal. High concentrations of As (200-1180 mug L-1) are accompanied by high concentrations of Fe (3-13.7 mgL(-1)) and PO4 (1-6.5 mg L-1). Ground water that is rich in Mn (1-5.3 mg L-1) contains

In some areas of Bangladesh and West Bengal, concentrations of As in groundwater exceed guide concentrations, set internationally and nationally at 10 to 50 m gl ˇ1 and may reach levels in the mg l ˇ1 range. The As derives from reductive dissolution of Fe oxyhydroxide and release of its sorbed As. The Fe oxyhydroxide exists in the aquifer as dispersed phases, such as coatings on sedimentary grains. Recalculated to pure FeOOH, As concentrations in this phase reach 517 ppm. Reduction of the Fe is driven by microbial metabolism of sedimentary organic matter, which is present in concentrations as high as 6% C. Arsenic released by oxidation of pyrite, as water levels are drawn down and air enters the aquifer, contributes negligibly to the problem of As pollution. Identification of the mechanism of As release to groundwater helps to provide a framework to guide the placement of new water wells so that they will have acceptable concentrations of As. # 2000 Elsevier Science Ltd. All rights reserved.

Sediment cores from Jellyfish Lake were processed under an inert atmos phcre and the pore waters extracted and analyzed for the following parameters: pH, titration alkalinity (TA), Cl-, H4Si04, POd3-, NH4+, Ca2+, Mg2+, SOd2-, and H2S. Additionally, in one set of pore-water samples (core lo), the 613C of the X0, was also determined. The TA, H4Si04, POd3-, NH;+, and H,S increased with depth in the pore waters above anoxic bottom-water values. H,S values increased to 3.8 PM. In one case, both H,SiO, and POd3- concentrations increased to a maximum value and then decreased with depth, suggesting removal into solid phases. The H,SiO, concentrations are equal to or greater than pore-water values observed in sediments underlying upwelling areas. Pod3 - concentrations are, in general, lower than pore-water values from terrigenous nearshore areas but higher than nearshore carbonate pore-water values from Florida Bay or Bermuda. The Ca2+, Cl-, and Mg2+ : Cl- ratios show slight decreases in the top 15-20 cm, suggesting that authigenic carbonate may be forming. This suggestion is supported by the fact that the pore waters are saturated with respect to CaCO, due to the very high TAs. The 613C measurements of the pore-water X0, are from a shorter core. These measurements reach their most negative concentration at 72 cm and tilen become slightly heavier. This change is accompanied by a decrease in TA, suggesting the onset of methanogenesis at this location in this core.

The distribution of As-pollution in groundwater of the deltaic aquifers of south-eastern Asia may be controlled by the subsurface distribution of palaeo-channel sediments (As-polluted groundwaters) and palaeo-interfluvial sediments (As-free groundwaters). To test this idea, termed the palaeosol model of As-pollution, we drilled 10 sites, analysed groundwater from 249 shallow wells (screened

Neodymium, samarium, and dysprosium concentrations were determined in groundwaters along a transect of Lake Gilmore sediments from the shoreline toward the playa center with the future intention of employing the whole suite of rare earth elements (REE). Two different water bodies were identified in the groundwater/playa system based on the neodymium, samarium, and dysprosium concentrations and associated pH and salinity values. Shallow groundwaters that discharge along the playa margins had the highest concentrations of these elements and the lowest pH and salinity. A more saline entrained brine was identified toward the middle of the playa with higher pH values and the lowest observed concentrations of neodymium, samarium, and dysprosium. Groundwaters with transitional neodymium, samarium, and dysprosium values, pH, and salinity were also recorded along the transect. The data suggest that the acidic shallow groundwaters remove REE from the surrounding granitic rocks of the Yilgarn block and introduce them into the playa where they are removed from solution as the pH of the system increases. Evaporative concentration does not appear to have a significant effect on the REE concentrations in the Lake Gilmore system. Other factors such as increasing pH and scavenging of REE by iron oxyhydroxides which precipitate as pH rises appear to exert more control on REE concentrations in the groundwaters by removing them from solution.

To reveal what controls the concentration and distribution of possibly hazardous (Mn, U, Se, Cd, Bi, Pb) and nonhazardous (Fe, V, Mo, PO(4)) trace elements in groundwater of the Bengal delta, we mapped their concentrations in shallow groundwater (60 mbgl) across 102 km(2) of West Bengal. Only Mn is a potential threat to health, with 55% of well water exceeding 0.3 mg/L, the current Indian limit for drinking water in the absence of an alternate source, and 75% exceeding the desirable limit of 0.1 mg/L. Concentrations of V are3 μg/L. Concentrations of U, Se, Pb, Ni, Bi, and Cd, are below WHO guideline values. The distributions of Fe, Mn, As, V, Mo, U, PO(4), and δ(18)O in groundwater reflect subsurface sedimentology and sources of water. Areas of less negative δ(18)O reveal recharge by sources of evaporated water. Concentrations of Fe, As, Mo, and PO(4) are high in palaeo-channel groundwaters and low in palaeo-interfluvial groundwaters. Concentrations of U, V, and Mn, are low in palaeo-channel groundwaters and high in palaeo-interfluvial groundwaters. Concentrations of Fe and Mn are highest (18 and 6 mg/L respectively) at dual reduction-fronts that form strip interfaces at depth around the edges of palaeo-interfluvial aquifers. The fronts form as focused recharge carries dissolved organic carbon into the aquifer margins, which comprise brown, iron-oxide bearing, sand. At the Mn-reduction front, concentrations of V and Mo reach peak concentrations of 3 μg/L. At the Fe-reduction front, concentrations of PO(4) and As reach concentrations 3 mg/L and 150 μg/L respectively. Many groundwaters contain10 mg/L of Cl, showing that they are contaminated by Cl of anthropogenic origin and that organic matter from in situ sanitation may contribute to driving reduction.

The consumption of groundwater polluted by arsenic (As) has a severe and adverse effect on human health, particularly where, as happens in parts of SE Asia, groundwater is supplied largely from fluvial/deltaic aquifers. The lateral distribution of the As-pollution in such aquifers is heterogeneous. The cause of the heterogeneity is obscure. The location and severity of the As-pollution is therefore difficult to predict, despite the importance of such predictions to the protection of consumer health, aquifer remediation, and aquifer development. To explain the heterogeneity, we mapped As-pollution in groundwater using 659 wells across 102 km(2) of West Bengal, and logged 43 boreholes, to reveal that the distribution of As-pollution is governed by subsurface sedimentology. Across 47 km(2) of contiguous palaeo-interfluve, we found that the shallow aquifer (70 mbgl) is unpolluted by As (10 μg/L) because it is capped by an impermeable palaeosol of red clay (the last glacial maximum palaeosol, or LGMP, of ref 1 ) at depths between 16 and 24 mbgl. The LGMP protects the aquifer from vertical recharge that might carry As-rich water or dissolved organic matter that might drive reduction of sedimentary iron oxides and so release As to groundwater. In 55 km(2) of flanking palaeo-channels, the palaeosol is absent, so invasion of the aquifer by As and dissolved organic matter can occur, so palaeo-channel groundwater is mostly polluted by As (50 μg/L). The role of palaeosols and, in particular, the LGMP, has been overlooked as a control on groundwater flow and pollutant movement in deltaic and coastal aquifers worldwide. Models of pollutant infiltration in such environments must include the appreciation that, where the LGMP (or other palaeosols) are present, recharge moves downward in palaeo-channel regions that are separated by palaeo-interfluvial regions where vertical recharge to underlying aquifers cannot occur and where horizontal flow occurs above the LGMP and any aquifer it caps.

In two distal carbonate turbidites (labelled a and e) from the Madeira Abyssal Plain oxidation of organic matter (OM) has been accompanied by a reduction in Hydrogen Index (HI) and change in the isotopic composition of carbon. Since the emplacement of turbidite α 0.5 ka ago 35% of the OM in the upper part has been oxidised by oxygen and nitrate diffusing from sea water into the sediment. There is an accompanying decrease of ≤ 0.3‰ in δ13C-OM, and a decrease of 25% in HI. Turbidite e was emplaced about 73 ka and was exposed to bottom water for 12.3 ka before being buried beneath later turbidites. During exposure oxygen and nitrate diffused into its upper part and oxidised 50% of the TOC without an accompanying change in isotopic composition; further oxidation of the more refactory organic components decreased TOC by a further 25% and decreased δ13C by 2.5‰. Oxidation also reduced HI by 50% from originally low values. Unless corrected for, the isotopic changes accompanying extended oxic and suboxic degradation of organic matter in sediments will give rise to erroneous estimates of marine-terrestrial OM ratios.

We report time-series data collected over two years for delta18O, delta2H, and Ca, Mg, K, and Cl, concentrations for 10 ponds in, and upflow of, an As-polluted region of southern West Bengal. We compare the compositions of As-polluted groundwaters from wells with the compositions of waters in ponds upflow, and within the range of influence, of the wells. Conservative tracers (delta18O, delta2H, K), and other tracers (Ca, Mg) that are likely conservative in the waters, showthat pondwater and groundwater are distinct and do not overlap in composition. These data show that water from ponds cannot be identified in As-polluted groundwater, so putative DOC in pondwater cannot be mixing into the As-polluted groundwater we have sampled. Separate estimates of the degree of recharge from ponds to groundwater, using calculations based on temporal variations in salt content and isotopic composition in ponds, and salt-balance, show that insignificant amounts of As-polluted groundwater are derived via pond recharge. It follows that pondwater in the study area does not contribute significant mass to arsenic-polluted groundwater and so does not provide organic matterto aquifers in amounts sufficientto drive reduction of iron oxyhydroxides and hence arsenic pollution.

In their comments on our paper1, both Acharyya et al. and Chowdhury et al. refer to previous suggestions2,3 that iron reduction might be the source of arsenic pollution. Naming a process2, suggesting that it occurs on the basis of reasoned argument3, and providing objective evidence that it does1,4 are different things.

Internal drainage in the south east of Western Australia are underlain by predominantly granitoid rocks. The regional shallow ground water are NaCl brines. Ratios of 87Sr/86Sr in the brines are 0.7155 ± 0.0015, which are close to the ratio of modern marine Sr (0.7092). A two-component isotopic mixing model, with end members of marine Sr and Sr from basement granitoid rocks, implies strongly that ⩽5% of the Sr is derived from rock weathering and ⩾95% is marine. The isotropic composition of S in gypsum crystallised from the brines is +19.8 ± 0.3ℵ CDT). This value is close to that of S in Recent evaporites (+21.5 ± 1CDT) and confirms that weathering of Archaean sulphides, with Δ34Sof0 ± 4ℵ (CDT), has contributed insignificant amounts of S to the brines. The isotopic data are compatible with a late Tertiary to Recent age for the Sr and S and, by implication, for the salts as a whole. The formation of alunite has been a major control on brine composition while gypsum and calcrete formation have been minor influences. None of the ground waters is saturated with halite which suggests the brines are immature and have evolved their present chemistry within the past few tens of thousands rather than millions of years. Marine aerosols are the main source of salt. Water sequestered in internal drainage basins, by a post-Middle Miocene regression, possibly provided a subordinate fraction.

Manganese can be rapidly determined in natural waters by direct-injection flameless a.a.s. Interference caused by sea salts in waters of salinity 0–35‰ can be eliminated by charring with ammonium nitrate and with a slow temperature rise. The sensitivity of the determination is depressed by the presence of nitric acid, the depression decreasing with graphite tube age. In saline water matrices, the detection limit is better than 0.002 ng and the sensitivity is better than 0.02 ng for 1% absorbance. Precision is better than 10% for manganese concentrations of 10 μg 1 -1 in sea water.

Several workers have recently reported the use of the formaldoxime method of Brewer and Spencer (1971) to analyse for Mn in seawater and pore water. According to Brewer and Spencer, the method requires a small correction for Fe interference, with 4.5/~M Fe being equivalent to 1.0/~M Mn. In seawater, and pore water from oxic abyssal sediments, Fe /Mn ratios are either reported to be, or are probably, _ 1 (Bacon et al., 1980; Kuivila and Murray, 1984; Emerson et al., 1984; some of Sanchez et al., 1986) the data may be in error if appropriate Fe corrections have not been applied. These authors give no details of Fe corrections and state (Sanchez excepted) only that the Mn analyses were done by the method of Brewer and Spencer (1971). Elsewhere, the method has been used to obtain Mn data, apparently without Fe corrections being applied (Murray et al., 1980; Jahnke et al., 1982; Kalhorn and Emerson, 1984; Thomson et al., 1986). In view of this, it is interesting to note that fig. 3a of Emerson et al. (1984) and fig. 3 (Station 2 data, particularly) of Kuivila and Murray ( 1984 ) show Mn profiles in which distinct breaks of slope correlate with the profiles of dissolved Fe: these Mn profiles may be distorted by inadequate correction for Fe interference. Sanchez et al. (1986) reported colorimetric concentrations of Mn some two to six times higher than AAS values. They attribute the difference to blank problems; inadequate Fe corrections may also contribute to the discrepancy. Bacon et al. (1980), however, reported good agreement between AAS and colorimetric analyses of Mn, albeit at concentrations of 0.5-25/1g/l-1, an order of magnitude less than those of Sanchez et al. The formaldoxime method for Mn analysis may, therefore, be subject to some problem from Fe interference where Fe is present in high concentrations, as it may be in suboxic pore water. In order to understand this interference its magnitude has been determined as a function of the time allowed for colour