The Maastricht Formation is a mostly calcarenitic unit that belongs to the Chalk Group but is unlike the typical North Sea chalk in that it is much coarser and at times contains a significant terrigenous component. The formation was deposited between the late Maastrichtian and the early Danian in a proximal zone of the Chalk Sea immediately north of the Anglo-Brabant and Rhenish massifs. The formation crops out in South Limburg, the Netherlands, in the German state of North Rhine–Westphalia, near Aix-la-Chapelle (Aachen), and in the Belgian provinces of Liège and Limburg, and it is present in the subsurface in the Campine Basin and in the Roer Valley Graben, in Belgium and the Netherlands.

The often spectacular fossil content of the Maastricht Formation has been extensively studied but its sedimentological aspects remain understudied. Indeed, the lithostratigraphy of the formation is largely informal and based on the abundance and morphology of flint and on the quantification of fossil content. The paucity of facies studies and the lack of a lithostratigraphic framework based on modern facies studies hampers stratigraphic correlation between outcrops and, more importantly, boreholes. A facies characterisation and facies-based lithostratigraphic framework of the Maastricht Formation in South Limburg is particularly urgent because groundwater is abstracted from aquifers in the formation and geological models currently in place fail to predict facies heterogeneity and, consequently, aquifer properties.

We studied eight outcrops of the Maastricht Formation across South Limburg and carried out a (micro)facies analysis of the outcrops. We show that the Maastricht Formation can be subdivided into three lithofacies and five microfacies. The lithofacies reflect the traditional subdivision of the formation into Maastricht and Kunrade limestones. Our results suggest that the current subdivision of the Maastricht Formation into six members is untenable. The formation is best subdivided into lower and upper members. The Kunrade limestone should be afforded the status of formation.

We interpret the Maastricht Formation as having been deposited in an epeiric ramp, in which facies distribution was controlled by water temperature, nutrient levels and storminess. The (micro)facies of the Maastricht Formation can be organised into two depositional stages: stage 1, representing the lower part of the formation, is characterised by heterozoan carbonates deposited under cooler, mesotrophic conditions in a nutrient-rich, more proximal region of the epeiric sea; stage 2 is characterised by heterozoan-photozoan carbonates deposited in a warmer and stormier environment with slightly lower nutrient levels.

Brachiopods from the lower upper Maastrichtian (Upper Cretaceous) white chalk succession exposed at Chełm (eastern Poland) comprise Lingula cretacea, Isocrania costata, Cryptoporella antiqua, Cretirhynchia sp., Neoliothyrina sp., Carneithyris sp., Terebratulina chrysalis, T. faujasi, T. longicollis, Terebratulina spp., Gisilina sp., Bronnothyris bronni, Magas chitoniformis, Leptothyrellopsis polonicus and ?Aemula sp. This assemblage is relatively poor in terms of taxonomic diversity and specimen abundance and is dominated by stratigraphically long-ranging species. It is best comparable to that from the micromorphic brachiopod Rugia tenuicostata–Meonia semiglobularis Zone as distinguished in the white chalk successions of Denmark and northern Germany, although this zone is usually placed in the upper lower Maastrichtian. The Chełm succession represents a relatively deep-water and ‘benthos-poor’ variety of white chalk deposited in the Boreal Chalk Sea of Europe. The brachiopod assemblage studied is typical of such a habitat, having been controlled largely by the low availability of minute skeletal substrates suitable for brachiopod settlement.

Upper Cretaceous—Danian chalk and interbedded clay-rich layers from wells of the South Arne Field and adjacent wells in the North Sea and from Stevns in Zealand have been investigated to determine the clay mineralogy in the chalk and the origin of the interbedded clay-rich layers. The mineralogy, with emphasis on clay mineralogy, was determined after removal of the calcite by dissolution at pH 4.5–5 in order to preserve the other minerals. Generally, mixed-layer minerals are the dominant clay minerals, except for two wells, Rigs-1 and Rigs-2, where a 3D ordered kaolinite prevails. A detailed structural characterization of the mixed-layer minerals was carried out by modeling of the X-ray diffraction (XRD) patterns. In most of the samples dominated by mixed-layer minerals, two mixed-layer phases, a high-smectite illite-smectite (I-S) and a low-smectite illite-smectite-chlorite (I-S-Ch), prevail, irrespective of depth or location of the samples. However, some samples contain I-S-Ch and ordered S-Ch, and others a chlorite-serpentine (Ch-Sr) phase, and these samples probably formed during diagenesis at higher temperatures. The clay-rich layers and the adjacent chalk have the same or quite similar clay mineralogy, both with respect to kaolinite vs. mixed-layer minerals and with respect to their detailed structure. In conclusion, the kaolinite is detrital and the I-S minerals formed in the chalk from volcanic ash. The main conclusion is that the clay-rich layers in the North Sea chalk formed by dissolution of the calcite in the chalk and that this dissolution took place at burial depths of >1 km, probably through migration of solutions through permeable chalk layers.

In contrast to the Norwegian and Danish sectors, where significant hydrocarbon reserves were found in chalk reservoirs, limited studies exist analysing the chalk evolution in the Dutch part of the North Sea. To provide a better understanding of this evolution, a tectono-sedimentary study of the Late Cretaceous to Early Palaeogene Chalk Group in the northern Dutch North Sea was performed, facilitated by a relatively new 3D seismic survey. Integrating seismic and biostratigraphic well data, seven chronostratigraphic units were mapped, allowing a reconstruction of intra-chalk geological events.

The southwestward thickening of the Turonian sequence is interpreted to result from tilting, and the absence of Coniacian and Santonian sediments in the western part of the study area is probably the result of non-deposition. Seismic truncations show evidence of a widespread inversion phase, the timing of which differs between the structural elements. It started at the end of the Campanian followed by a second pulse during the Maastrichtian, a new finding not reported before. After subsidence during the Maastrichtian and Danian, renewed inversion and erosion occurred at the end of the Danian. Halokinesis processes resulted in thickness variations of chalk units of different ages.

In summary, variations in sedimentation patterns in the northern Dutch North Sea relate to the Sub-Hercynian inversion phase during the Campanian and Maastrichtian, the Laramide inversion phase at the end of the Danian, and halokinesis processes. Additionally, the Late Cretaceous sea floor was characterized by erosion through contour bottom currents at different scales and resedimentation by slope failures.

The structure of an illite-smectite (I-S) sample (HSI) from the Tertiary–Cretaceous boundary layer at Stevns, Denmark, i.e. the so-called Fish Clay, is investigated in order to discuss the origin of this clay and its similarity to clays from Maastrichtian-Danian chalk of Denmark and the North Sea. The phase compositions and layer sequences have been determined by X-ray diffraction. The structural formulae are determined from chemical analysis and solid-state 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The octahedral vacancy pattern has been determined by thermal analysis and the particle shape by atomic force microscopy. The HSI sample I-S consists of two phases, a high-smectitic (HS) phase (70%) having 95% smectite and 5% illite (leucophyllite) layers, and a low-smectitic (LS) phase (30%) having 50% smectite and 50% illite (leucophyllite) layers. Both phases have trans-vacant dioctahedral sheets and contain only traces of IVAl, the charge of the illite (leucophyllite) layers being provided predominantly by octahedral Mg for Al substitution. The structure of the tetrahedral and octahedral sheets for the HSI are compared to the structure of an I-S sample (GRI) from the Maastrichtian chalk at Stevns below the Tertiary-Cretaceous boundary and to the standard smectite SAz-1 from Arizona. For all three samples the 27Al MAS NMR spectra show the presence of two resolved IVAl resonances, which indicate the presence of two different IVAl sites. The NMR, infrared spectroscopy and chemical data show that both HSI and GRI have highly ordered Mg for Al substitution in the octahedral sheet, each Al having one Mg and two Al neighbours, whereas substitution of Mg for Al in SAz-1 is random. For the HSI sample, both the HS and LS phases are probably formed from volcanic ash. The structural similarity of the phases in HSI and GRI shows that GRI formed from a material similar to HSI by illitization of the HS phase and chloritization of the LS phase.

In the Upper Cretaceous-Danian North Sea chalk, silica composed of nano-size quartz spheres is dispersed in the chalk matrix, and quartz is present in bands and nodules of flint. In the present investigation of the North Sea Danian chalk the nano-quartz in the chalk matrix is compared with the silica in the flint. Samples of chalk and flint layers from four North Sea wells have been investigated. Atomic Force Microscopy (AFM) has been applied to image the quartz in the chalk and in the flint. X-ray diffraction (XRD), including analysis of the positions and profiles of hkl reflections in powder diffraction patterns, has been applied to characterize the lattice of the quartz in both the chalk matrix and in the flint. The quartz in the chalk matrix and in the flint is composed of nano-quartz spheres having identical cell parameters. Based on the results we propose a new model for formation of flint in North Sea chalk: (1) The nano-quartz in the flint, like the nano-quartz in the chalk matrix, has crystallized in the marine Chalk Sea environment. The colloidal quartz particles flocculated and were deposited on the sea floor mixed with calcitic bioclastic material. (2) Regional variations in the concentration of nano-quartz particles in the sediment reflect different degrees of acidification of the Chalk Sea. (3) This resulted in areas where practically all the calcite bioclasts were dissolved leaving a high concentration of nano-quartz particles to form flint layers; where there was less dissolution, indurated chalk with abundant nano-quartz particles is now preserved. (4) The acidification could have been caused by the effects of enhanced atmospheric CO2 linked to massive short-lived volcanic eruptions in the British Tertiary Igneous Province.

In the oil fields in the Central Graben of the North Sea, Maastrichtian chalk is an important hydrocarbon reservoir, but oil may also be found in the Danian chalk, consisting of white chalk interbedded with clay layers. Within the chalk section, discrete intervals appear like chalk but contain large amounts of quartz (up to 100%). The aim of the present investigation is to reveal the mechanism for formation of the quartz in these intervals and to discuss their regional distribution and importance for the reservoir properties. Samples of chalk, including quartz-rich intervals, and clay layers from three wells SA-1, Rigs-1 and Rigs-2 in the South Arne Field have been investigated. Calcite-free residues obtained using a buffered dissolution of calcite were investigated using X-ray diffraction, scanning electron microscopy and atomic force microscopy. The main silica phase in the Upper Cretaceous–Danian chalk in the three wells is a nano-size α-quartz. This has probably formed from Si dissolved from radiolarians in the free-water phase. The 600 Å diameter α-quartz spheres precipitated in the free-water phase with subsequent flocculation of the spheres and sedimentation of the flocs. Variations in the proportion of quartz in the chalk are attributed to variations in the amount of radiolarians in combination with variations in CO2 concentrations in the water; increased CO2 causes dissolution of coccoliths and thus a relative enrichment in quartz. This formation mechanism is regional and makes it probable that the layers rich in nano-quartz may be found over large areas provided that the chalk is authigenic. Quartz-rich layers are generally of low permeability and in areas with authigenic chalk these layers may act as internal seals in chalk reservoirs.

Illite-smectite (I-S) mixed-layer minerals from North Sea oil fields and a Danish outcrop were investigated to determine the detailed structure and the diagenetic clay transformation. Clay layers in the chalk and residues obtained by dissolution of the chalk matrix at pH 5 were investigated. The phase compositions and layer sequences were determined by X-ray diffraction (XRD) including simulation with a multicomponent program. The structural formulae were determined from chemical analysis, infrared (IR) and 27Al NMR spectroscopies and XRD, and the particle shape by atomic force microscopy (AFM). A high-smectitic (HS) I-S phase and a lowsmectitic (LS) illite-smectite-chlorite (I-S-Ch) phase, both dioctahedral, together constitute 80 – 90% of each sample. However, two samples contain significant amounts of tosudite and of Ch-Serpentine (Sr), respectively. Most of the clay layers have probably formed by dissolution of the chalk, but one Campanian and one Santonian clay layer in well Baron 2 may have a sedimentary origin. The HS and LS minerals are probably of detrital origin. Early diagenesis has taken place through a fixation of Mg in brucite interlayers in the LS phase, this solid-state process forming di-trioctahedral chlorite layers. During later diagenesis involving dissolution of the HS phase, neoformation of a tosudite or of a random mixed-layer trioctahedral chlorite-berthierine took place. In the tosudite, brucite-like sheets are regularly interstratified with smectite interlayers between dioctahedral 2:1 layers, resulting in ditrioctahedral chlorite layers.

A zeolite found in a soil profile developed in Danian chalk was studied. The results showed that it is a heulandite, temperature-stable to above 600°C with a Si/Al ratio of 2.88 and almost completely K-exchanged. The mineral probably formed under burial diagenetic conditions in the chalk formation.

Degradation of contaminant hydrocarbons in groundwater by microbially mediated oxidation, linked to the reduction of electron acceptors, is fundamental to the strategy of ‘monitored natural attenuation’ (MNA) for oxidizable hydrocarbons, which is increasingly being adopted at polluted aquifer sites throughout Europe and North America. Commonly, oxygen is depleted and following the reduction of nitrate, solid-phase Fe oxides become the dominant electron acceptors. Arsenic, associated with Fe and Mn oxides in soils and sediments, may therefore be mobilized to groundwater and pose an additional threat to environmental receptors. In a pilot study of three aquifers in England, we have examined the extent to which arsenic is released to groundwater under Fe(III)-reducing conditions imposed by contaminant hydrocarbons. Results show that arsenic is locally mobilized in the Chalk to <10 μg/1, in Quaternary gravels to 70 μg/1 and in the Triassic sandstones to 160 μg/1. At the Chalk and Quaternary gravels sites arsenic mobilization is demonstrably linked to reduction of Fe- and Mn-oxides. This is not so at the Triassic sandstone site, where release of arsenic is related to elevated bicarbonate alkalinity. Redox-driven arsenic mobilization at other Triassic sandstone locations is possible. Further work is required on the solid-phase sources of arsenic in the aquifers, and to relate the hydrochemical observations to groundwater hydraulic conditions.

The idea is tested that the evolution of the Chalk’s clay mineral assemblage during diagenesis can be deduced by examining the relationships between its clay mineralogy, particle size distribution pattern, and the timing and trace element chemistry of the calcite cement. The preliminary results from five different examples of cementation developed at different stages of diagenesis in chalks with smectite-dominated clay assemblages suggest that this is a promising line of investigation. Soft chalks with minor amount of anoxic series calcite cement poor in Mg, Fe and Mn are associated with neoformed trioctahedral smectite and/or dioctahedral nontronite and talc. Hard ground chalk with extensive anoxic series calcite cement enriched in Mg and relatively high Fe, Mn and Sr are associated with neoformed glauconite sensu lato, berthierine and dioctahedral smectite, possibly enriched in Fe. The chalk associated with large ammonites shows extensive suboxic series calcite cement enriched in Mg, Mn and Fe that show no obvious correlation with its clay mineralogy. Nodular chalks with patchy suboxic series calcite cement enriched in Fe are associated with neoformed dioctahedral smectite, possibly enriched in Al, and berthierine. Regionally hardened chalk with extensive suboxic calcite cement and relatively high trace element contents contain pressure dissolution seams enriched in kaolin and berthierine. Laser-based particle-size distribution patterns suggest that each type of lithification has a typical complex clay mineral population, indicating that subtleties in mineralogy are not being identified and that there could be some control on the size and shape of the clay crystals by the different types of cementation.

Detrital, volcanic and diagenetic origins have been used to explain the smectite clay assemblage that characterizes the Upper Cretaceous Chalk of Europe. To further the understanding of how clays of different origins may have converged to this characteristic clay mineral assemblage a new approach is put forward for their investigation. This is based upon (1) the correlation that exists between the trace element and stable isotope geochemistry of the calcite cements preserved within Chalk brachiopods and the various diagenetic phases of early lithification and cementation recognized in the Chalk, and (2) an understanding of the process of late diagenetic cementation that has caused regional differences in the hardness of the Chalk. It is suggested that each phase of lithification and associated calcite cementation may preserve the different clay assemblages at various stages in their convergence to the characteristic Chalk smectite assemblage.

Very hard cemented chalk stacks and crusts found locally in the upper part of the Cretaceous Chalk of north Norfolk, UK, are related to solution features. The solution features, mainly pipes and caves, formed after deposition of the overlying Middle Pleistocene Wroxham Crag, probably by routing of sub-glacial, or glacial, melt-waters derived from late Pleistocene glaciers. New geochemical (particularly stable isotope) data shows that cementation of the chalks, although related spatially to the solution features, was not caused by glacier-derived waters. The carbon isotope composition of the chalk cements is typically around −9.5‰, indicative of biologically active soils. Moreover, the oxygen isotope compositions of the cements, around −5‰, are incompatible with water δ18O values much below −9 to −10‰ (which probably precludes isotopically negative glacier-derived water), as resulting palaeo-temperatures are below zero. Taken together, the isotope data suggest chalk cementation occurred under interglacial conditions similar to the present. Dissolved calcium carbonate for cementation came from dissolution of reworked chalk in overlying MIS 12 glacial tills.

Carbon stable-isotope variation through the Cenomanian–Santonian stages is characterized using data for 1769 bulk pelagic carbonate samples collected from seven Chalk successions in England. The sections show consistent stratigraphic trends and δ13C values that provide a basis for high-resolution correlation. Positive and negative δ13C excursions and inflection points on the isotope profiles are used to define 72 isotope events. Key markers are provided by positive δ13C excursions of up to +2‰: the Albian/Cenomanian Boundary Event; Mid-Cenomanian Event I; the Cenomanian/Turonian Boundary Event; the Bridgewick, Hitch Wood and Navigation events of Late Turonian age; and the Santonian/Campanian Boundary Event. Isotope events are isochronous within a framework provided by macrofossil datum levels and bentonite horizons. An age-calibrated composite δ13C reference curve and an isotope event stratigraphy are constructed using data from the English Chalk. The isotope stratigraphy is applied to successions in Germany, France, Spain and Italy. Correlation with pelagic sections at Gubbio, central Italy, demonstrates general agreement between biostratigraphic and chemostratigraphic criteria in the Cenomanian–Turonian stages, confirming established relationships between Tethyan planktonic foraminiferal and Boreal macrofossil biozonations. Correlation of the Coniacian–Santonian stages is less clear cut: magnetostratigraphic evidence for placing the base of Chron 33r near the base of the Upper Santonian is in good agreement with the carbon-iso-tope correlation, but generates significant anomalies regarding the placement of the Santonian and Campanian stage boundaries with respect to Tethyan planktonic foraminiferal and nannofossil zones. Isotope stratigraphy offers a more reliable criterion for detailed correlation of Cenomanian–Santonian strata than biostratigraphy. With the addition of Campanian δ13C data from one of the English sections, a composite Cenomanian–Campanian age-calibrated reference curve is presented that can be utilized in future chemostratigraphic studies.

The Cenomanian–Campanian carbon-isotope curve is remarkably similar in shape to supposedly eustatic sea-level curves: increasing δ13C values accompanying sea-level rise associated with transgression, and falling δ13C values characterizing sea-level fall and regression. The correlation between carbon isotopes and sea-level is explained by variations in epicontinental sea area affecting organic-matter burial fluxes: increasing shallow sea-floor area and increased accommodation space accompanying sea-level rise allowed more efficient burial of marine organic matter, with the preferential removal of 12C from the marine carbon reservoir. During sea-level fall, reduced seafloor area, marine erosion of previously deposited sediments, and exposure of basin margins led to reduced organic-carbon burial fluxes and oxidation of previously deposited organic matter, causing falling δ13C values. Additionally, drowning of carbonate platforms during periods of rapid sea-level rise may have reduced the global inorganic relative to the organic carbon flux, further enhancing δ13C values, while renewed platform growth during late transgressions and highstands prompted increased carbonate deposition. Variations in nutrient supply, changing rates of oceanic turnover, and the sequestration or liberation of methane from gas hydrates may also have played a role in controlling carbon-isotope ratios.