Erratum to “The Albian-Cenomanian boundary at Eggardon Hill, Dorset (England): An anomaly resolved?” [Proc. Geol. Assoc. 120 (2009) 108-120]

Re-examination of the classic exposures of the Eggardon Grit (topmost Upper Greensand Formation) at Eggardon Hill, Dorset shows that the upper part of this unit has a more complex stratigraphy than has been previously recognised. The Eggardon Grit Member, as described herein, is capped by a hardground and associated conglomerate, and is entirely of Late Albian age. The hardground is probably the lateral equivalent of the Small Cove Hardground, which marks the top of the Upper Greensand succession in southeast Devon. The conglomerate is overlain by a thin sandy limestone containing Early Cenomanian ammonites. This limestone is almost certainly the horizon of the Early Cenomanian ammonite fauna that has previously been attributed to the top of the Eggardon Grit. The limestone is regarded as a thin lateral equivalent of the Beer Head Limestone Formation (formerly Cenomanian Limestone) exposed on the southeast Devon coast. The fauna of the limestone at Eggardon suggests that it is probably the age equivalent to the two lowest subdivisions of the Beer Head Limestone in southeast Devon, with a remanié fauna of the Pounds Pool Sandy Limestone Member combined with indigenous macrofossils of the Hooken Nodular Limestone Member. The next highest subdivision of the Beer Head Limestone in southeast Devon (Little Beach Bioclastic Limestone Member), equates with the ammonite-rich phosphatic conglomerate of the ‘Chalk Basement Bed’, which caps the Beer Head Limestone at Eggardon, and which was previously regarded as the base of the Chalk Group on Eggardon Hill.Petrographic analysis of the Eggardon Grit shows that lithologically it should more correctly be described as a sandy limestone rather than sandstone. The original stratigraphical definition of the unit should probably be modified to exclude the softer, nodular calcareous sandstones that have traditionally been included in the lower part of the member.Without the apparently clear evidence of unbroken sedimentation across the Albian-Cenomanian boundary, suggested by the previous interpretation of the Eggardon succession, it is harder to argue for this being a prevalent feature of Upper Greensand stratigraphy in southwest England. Correlation of the Eggardon succession with successions in Dorset and southeast Devon reveals a widespread regional break in sedimentation at the Albian-Cenomanian boundary. The sand-rich facies above this unconformity represent the true base of the Chalk Group, rather than the ‘Chalk Basement Bed’ of previous interpretations.Selected elements of regionally important Upper Greensand ammonite faunas previously reported from Shapwick Quarry, near Lyme Regis, and Babcombe Copse, near Newton Abbot, are newly figured herein.     

The Cenomanian–Turonian boundary on the Saharan Platform (Tunisia and Algeria)

Several transects made of correlated stratigraphic sections and well logs have been constructed spanning southern Tunisia and the Algerian Sahara (Tinrhert) for comparison with earlier results obtained in the Saharan Atlas. The study is based on facies analysis, sedimentology, biostratigraphy focused on ammonites and foraminifers) as well as whole rock geochemistry (δ¹³C). These suggest that the entire northern Sahara Platform underwent marine flooding that commenced just prior to the onset of the global positive δ¹³C shift documented for the Cenomanian–Turonian boundary. This flooding occurred in two phases. The first phase is expressed by the deposition of deeper-water, light-coloured bioturbated mudstones overlying the shallow-water deposits comprising the local Cenomanian successions. But in some places in the Central Sahara (Hassi Messaoud area, Tihemboka Arch) as well as in the Saharan Atlas, shallow-water carbonates kept up locally with the relative sea-level rise to build up isolated carbonate platforms. The topographic lows or saddles between these areas could have been formed through differential accumulation rates. During the second phase, flooding resumed and black shales were deposited over the mudstones in the saddles. The occurrence of black shales in these saddles is limited to the northern edge of the platform (Saharan Atlas of Algeria, Gafsa Trough in southern Tunisia). On the platform, this phase is represented by the same kind of mudstones deposited during the first phase of the flooding (southern Tunisia), or by ammonite-rich chalks in the intra-cratonic basin of the Tinrhert (southern Algeria). Black-shale deposition ceased in the early Turonian. Based on the δ¹³C curve, the latest Cenomanian flooding of the Sahara Platform is roughly coeval with that documented for the US Western Interior.During the first phase of the transgression, that is before the occurrence of the large Whiteinella of the W. archeocretacea Zone in the black shale unit, planktic foraminifers are dominated by small globulose forms of the Hedbergella delrioensis type, associated with Heterohelicidae. Keeled forms (rotaliporids, dicarinellids) are scarce and always very small when present. Perhaps these dwarfed forms were adapted to the restricted environments of the extensive intracratonic seaways crossing the Saharan Platform to the Benoué Trough in Nigeria.     

Albian–Cenomanian Granitoid Magmatism and Copper Ore Genesis in Sikhote-Alin (Far East,Russia)

Doklady Earth Sciences - The Late Albian–Early Cenomanian epoch of Au-Cu porphyry ore mineralization has been distinguished within the Sikhote-Alin. The development of ore mineralization is...     

Mid-Cretaceous (Albian–Cenomanian) fossil woods from Hwawon-myeon in Jeollanam-do,Korea, and their palaeoclimatic implications

Two coniferous fossil wood taxa are reported from the Hwawon Formation (middle Cretaceous) at Hwawon-myeon in Jeollanam-do, Korea: Agathoxylon sp. and Taxodioxylon sp. Agathoxylon has a clear affinity with the Araucariaceae and its occurrence in the Hwawon Formation suggests that a dry and tropical–subtropical climate prevailed in this area during the middle Cretaceous. The presence of traumatic resin canals in the Taxodioxylon specimens indicates that flooding occurred repeatedly as part of an alternation between dry and rainy seasons. The low diversity observed for the Cretaceous fossil wood assemblages from the Korean Peninsula could be explained by the palaeoclimatologically stressful environment, as a dry tropical–subtropical climate prevailed over the region at that time.     

The palynology and geology of the Lower Cretaceous (Aptian–Albian) of Munday’s Hill Quarry,Bedfordshire, UK

Early Cretaceous sediments of Aptian–Albian age outcrop at Munday’s Hill Quarry, Bedfordshire, England. Previous papers describing the section have resulted in different terminologies being applied. The Lower Cretaceous in Bedfordshire is represented by sediments belonging to the Lower Greensand Group and the Gault Clay Formation. Within the Lower Greensand Group in the study area the Woburn Sands Formation, are of Aptian–Albian age. Selected samples have been analysed for palynology. The analysis reveals diverse palynomorph assemblages, including well-preserved dinoflagellate cysts and sporomorphs. Comparison of the assemblages with published records indicates that the lower samples are of Late Aptian age. Forms recorded include common Kiokansium unituberculatum, Cerbia tabulata, Aptea polymorpha and Cyclonephelium inconspicuum. An Early Albian age is indicated for the uppermost sample.     

Planktonic foraminiferal biostratigraphy and assemblage composition across the Cenomanian–Turonian boundary interval at Clot Chevalier (Vocontian Basin,SE France)

The Cenomanian–Turonian boundary interval is generally considered a critical time for planktonic foraminifera due to the environmental perturbations associated with Oceanic Anoxic Event 2. However, only the rotaliporids became extinct at the onset of the event, whilst several lineages evolved and/or diversified. This remarkable morphologic plasticity is often overlooked in the literature, partly because a number of stratigraphic sections have only been studied in thin-section due to the degree of lithification of the samples. Improved documentation of the morphological variability of planktonic foraminifera and better defined species concepts are required in order to improve biostratigraphy, particularly as Helvetoglobotruncana helvetica is an unreliable marker for the base of the Turonian. At the same time, detailed study of the planktonic foraminiferal response to OAE 2 demands a more profound knowledge of the assemblage composition.We present new biostratigraphic, taxonomic, and quantitative data for planktonic foraminiferal species from the Clot Chevalier section (Vocontian Basin, SE France), with the aim of (1) providing a detailed biostratigraphic analysis of the section, (2) documenting the morphological plasticity of specimens in this time interval and stabilizing species concepts, and (3) identifying promising markers to improve the resolution of the present biozonation and allow regional correlation. Samples were processed with acetic acid to extract isolated planktonic foraminifera. Assemblages were assigned to the upper Cenomanian Rotalipora cushmani Zone and to the uppermost Cenomanian–lowermost Turonian Whiteinella archaeocretacea Zone. Planktonic foraminiferal bioevents and assemblage composition identified at Clot Chevalier are compared with the well-studied Pont d'Issole section located ca. 15 km to the NE, highlighting similarities and differences in the species occurrences that may complicate the stratigraphic correlation between the two sections.The results of our study support the validity and common occurrence of species that have been misidentified and/or overlooked in the literature (i.e., Dicarinella roddai, Praeglobotruncana oraviensis, Marginotruncana caronae) and indicate that primitive marginotruncanids evolved before the onset of OAE 2, although species diversification occurred only after the event. Moreover, we believe that the first appearance of P. oraviensis might represent a promising bioevent for approximating the Cenomanian/Turonian boundary, after calibration with bio- and chemostratigraphically well-constrained sections. Finally, we describe three new trochospiral species, named “Pseudoclavihedbergella” chevaliensis, Praeglobotruncana pseudoalgeriana and Praeglobotruncana clotensis.     

Organic geochemistry and petrography of Kazhdumi (Albian–Cenomanian) and Pabdeh (Paleogene) potential source rocks in southern part of the Dezful Embayment,Iran

There are several source rock units in the Zagros Basin, but the Cretaceous Kazhdumi and Paleogene Pabdeh formations probably have produced the majority of the commercial hydrocarbons in this area. Among the hydrocarbon provinces of Iran, the Dezful Embayment, which is located southwest of Zagros Mountains, is one of the most prolific regions in the Middle East. Numerous studies have been made in the northern part of the Dezful Embayment, but relatively few have been done in its southern part. The present study focuses on organic matter characterization of two potential source rocks (Kazhdumi and Pabdeh formations) in southern part of the Dezful Embayment. Cuttings samples (114) were collected from 10 wells and evaluated using Rock–Eval pyrolysis and organic petrography in order to characterize the content and type of organic matter and thermal maturity. The results showed that the average total organic carbon (TOC) content of Kazhdumi and Pabdeh formations are 2.48 and 1.62 wt%, respectively. The highest TOC contents for both formations are found in the northern compartment and decreased gradually toward the south. Pyrolysis data reveal that organic matter has a fair to very good hydrocarbon generation potential and are classified as Type II–III and Type III. Rock–Eval T_max and vitrinite reflectance show that the majority of samples are in the early mature to mature stage of the oil generation window.     

A new Cenomanian vertebrate tracksite at Tamajón (Guadalajara,Spain): Palaeoichnology and palaeoenvironmental implications

A new Upper Cretaceous vertebrate tracksite has been discovered at Tamajón (Iberian Ranges, Guadalajara, Spain). The track level is a relatively smooth and slightly undulating sandy ferruginous crust, corresponding to an erosive surface at the base of a small meandering channel. It is incised into the underlying planar cross-bedded sandstones of coastal bars located at the middle-upper part of the Utrillas Formation (middle-upper Cenomanian). The site shows an extraordinary concentration of vertebrate tracks, among which numerous sets of two to five isolated digit impressions (“swim tracks”) and, at least, two trackways referred to crocodyliforms, and a single tridactyl footprint probably produced by a theropod dinosaur can be recognized. There are also several long traces (epichnial grooves) revealing sharp direction changes (up to 90°) which seem to be fish fin traces (Undichna unisulca), although crocodyliforms (tail marks) and/or fish invertebrates cannot be rejected as possible tracemakers. Some crocodyliform tracks reveal a thin raised rim, due to the displacement of the sediment by the pressure produced by the feet. Several impressions are moderately deformed by small sediment slides, only preserving their deepest part (claw marks). This is clearly indicative of a soft substrate with a high degree of plasticity and water content at the time of the track registration. Nevertheless, the sediment was hard enough to preserve manus and pes print morphologies and also possible crocodyliform tail and/or fish fin traces. Small rhizoliths can also be recognized and may belong to herbaceous wetland vegetation. The morphology of the palaeochannel, the sedimentary context and the track preservation seem to indicate that the tracks were impressed in a shallow channel located near the coast, under wet conditions and in different moments of time. This discovery represents the first occurrence of vertebrate ichnites in the Utrillas Formation, a stratigraphic unit where osteological and ichnological remains are relatively scarce, and it confirms that some crocodyliforms lived in near coast channels during the deposition of this unit.     

Integrated stratigraphy across the Aptian/Albian boundary at Col de Pré-Guittard (southeast France): A candidate Global Boundary Stratotype Section

The outcrop of the Marnes Bleues at the Col de Pré-Guittard, 11 km north of the village of Rémuzat in the Départment of Drôme in southeastern France is probably the most intensively studied succession spanning the Aptian/Albian boundary interval. Following the rejection of the proposed GSSP for the base of the Albian Stage (based on the first occurrence of the ammonite Leymeriellla tardefurcata in the section at Le Pillart, Tartonne, Alpes-de-Haute Provence), we re-visit the Pré-Guittard section. A new candidate GSSP defined by the first occurrence of the planktonic foraminifera Microhedbergella renilaevis Huber and Leckie, 2011 is here proposed. This first occurrence is placed in a 100 m section with 28 secondary markers, including calcareous nannofossils, planktonic foraminifera, palynomorphs, an inoceramid bivalve, ammonites, stable carbon isotopes, and local marker beds. The outcrop fulfils most of the physical criteria required of a Global Stratotype Section and Point.     

The most ancient member of the Sequoioideae – the new genus Krassilovidendron Sokolova,Gordenko et Zavialova (Cupressaceae s.l.) from the Albian–Cenomanian of Western Siberia (Russia)

The new genus Krassilovidendron Sokolova, Gordenko et Zavialova with the type species Krassilovidendron fecundum Sokolova, Gordenko et Zavialova is described on the basis of numerous compressions of polymorphic shoots in organic connection with seed and pollen cones from the Albian–Cenomanian of the Kubaevo locality (Russian Federation, Kemerovo region, Western Siberia). The new taxon is characterized by an assemblage of features that distinguishes it from all known extant and fossil conifer genera: shoots with helically arranged leaves varying from amphistomatic small scale-like leaves to strictly epistomatic linear-lanceolate leaves; terminal, ellipsoidal to obovate seed cones, bearing 14–26 helically arranged peltate bract-scale complexes (bract and ovuliferous scale are completely fused) with a cylindrical vascular bundle, bifurcating into abaxial and adaxial dichotomizing bundles; up to 22 inverted seeds of various shapes with a protruding micropyle and inconspicuous lateral wings, which are arranged in two to five arcuate rows; solitary terminal pollen cones with helically arranged microsporophylls, each bearing four abaxial microsporangia; and small pollen grains with a relatively short papilla, numerous orbicules on the surface, and a three-layered ectexine with a tectum of strongly fused granules, an infratectum of smaller and more loosely arranged granules, and a thin footlayer. The new taxon possesses a combination of characters indicating it belongs to the subfamily Sequoioideae. Krassilovidendron shares the greatest number of features with Sequoia Endlicher and Sequoiadendron Buchholz, and fewer characters with Metasequoia Miki ex Hu et W.C. Cheng.     

The Redan Geophysical Zone: Part of the Willyama Supergroup? Broken Hill,Australia

The Redan Geophysical Zone forms a regional magnetic high in contrast to the regional magnetic low defined by the main part of the Broken Hill Block. The magnetic rocks are interpreted to dip below the remainder of the Broken Hill Block and there has been speculation that they are significantly older than the Early Proterozoic Willyama Supergroup.

Evaluation of lithological mapping and aeromagnetic data permitted interpretation of a stratigraphic sequence within the Redan Geophysical Zone, consisting of three new formations: the Redan Gneiss, Ednas Gneiss and Mulculca Formation, plus the Lady Brassey Formation, part of the Thackaringa Group. The rocks are considered to belong to the lower part of the Willyama Supergroup and are not an older basement.

Although the Redan Geophysical Zone contains some rock types not found elsewhere in the Broken Hill Block, there are some lithological similarities with the lower part of the Willyama Supergroup: an abundance of albite‐rich rocks, the presence of quartz‐magnetite rocks with Cu and trace Co, and abundant amphibolite/ basic granulite in the Lady Brassey Formation.

The boundary between the Redan Geophysical Zone and the remainder of the Broken Hill Block appears to be conformable, with no evidence of major faulting. Similarly no evidence of unconformities or major displacement of stratigraphic boundaries has been found within the Redan Geophysical Zone. Structural history, fold style and orientation, and metamorphic grade within the Redan Geophysical Zone are similar to adjacent areas of the Broken Hill Block.

It is concluded that the Broken Hill Block contains no outcropping equivalent of the first cycle of sedimentary/ igneous rocks recognized in the Early Proterozoic of northern Australia.

Albite‐quartz‐hornblende‐magnetite rocks unique to the Redan Geophysical Zone most likely comprised detritus derived directly from an intermediate volcanic suite. Some were altered considerably, while other rocks retained the dacite/andesite composition, except for the addition of Na, an increase in the oxidation state, and partial leaching of some of the more mobile elements. These modifications could have taken place in shallow alkaline evaporitic lakes.

The Redan Geophysical Zone contains some of the elements of a foreland basin adjacent to a continental volcanic arc: a thick stratigraphic sequence, oxidizing evaporitic conditions, and intermediate volcanic detritus. The change from intermediate‐acid volcanism in the earliest formations, to bimodal acid/basic volcanism in the Thackaringa and Broken Hill Groups could correspond with a change from initial continental arc volcanism into bimodal rift volcanism. The case for the arc volcanism is weakened, however, by the relative scarcity of rocks with andesitic compositions and the lack of basaltic andesite compositions. The alternative is that the intermediate to acid volcanism represents only a variation on the later bimodal rift volcanism.     

Barremian–Albian (Early Cretaceous) ammonite faunas of the Katsuuragawa Basin,southwest Japan

The Lower Cretaceous ammonite fauna of Japan was influenced by the Tethyan, Boreal and North Pacific realms with their oceanic current patterns and ammonite distributions. The hypothesis of oceanic circulation can be utilized to interpret the existence of the “Bering Strait” and the changing position of the “Boreal front,” that is the contact region of warm and cold-water masses. To understand such a system fully, a comprehensive understanding of the geographical distribution of ammonite faunas is required. The occurrence of twenty-five ammonite species, belonging to twenty genera, is confirmed in the Barremian to Albian of Japan. Of these, 24 species are described in this paper, including Barremites macroumbilicus sp. nov. The fauna can be divided into three associations, lower, middle, and upper, indicating late Barremian, late Aptian, and late Albian of the European standard zonation. The faunal characters suggest that the habitats of these ammonite faunas may have changed during later Early Cretaceous, with faunas characterizing three different environments, i.e., nearshore, intermediate, and distal shelf to upper slope setting. Ammonites of the lower association (late Barremian) are related to those of the Tethys, Boreal European, and circum-Pacific regions, and suggest that the Early Cretaceous Katsuuragawa Basin was deposited under the influence of currents from both high latitude and equatorial areas. The occurrence of Crioceratites (Paracrioceras) suggests that the Boreal European elements, including Simbirskites and Crioceratites (Paracrioceras), transited between Northwest Europe and Japan through the Arctic Sea, indicating that the Pacific Ocean was connected with the Arctic Sea at that time. The second association (late Aptian) is composed of ammonites of the Tethyan and circum-Pacific regions. As European Boreal ammonite taxa are absent in this association, it is concluded that the Pacific Ocean probably was not connected with the Arctic Sea at the time. Consequently, the “Boreal Front,” marking the contact between warm and cold water masses, was located at mid-latitude in the “Bering Strait” region during Barremian and subsequently moved northward during Albian. The uppermost ammonite association (late Albian) also consists of Tethyan and circum-Pacific taxa. Desmoceras (Pseudouhligella) poronaicum expanded its range with northward and eastward circulation of oceanic currents, suggesting the current must have represented a warm water-mass from the equator. The species subsequently migrated from the southern Katsuuragawa Basin to the Hokkaido area during late to latest Albian.     

The terminal Permian in European Russia: Vyaznikovian Horizon,Nedubrovo Member,and Permian–Triassic boundary

The comprehensive analysis of the data obtained on terrestrial vertebrata, ostracods, entomologic fauna, megaflora, and microflora in deposits of the Vyaznikovian Horizon and Nedubrovo Member, as well as the paleomagnetic data measured in enclosing rocks, confirms heterogeneity of these deposits. Accordingly, it is necessary to distinguish these two stratons in the terminal Permian of the East European Platform. The combined sequence of Triassic–Permian boundary deposits in the Moscow Syneclise, which is considered to be the most complete sequence in the East European Platform, is as follows (from bottom upward): Vyatkian deposits; Vyaznikovian Horizon, including Sokovka and Zhukovo members; Nedubrovo Member (Upper Permian); Astashikha and Ryabi members of the Vokhmian Horizon (Lower Triassic). None of the sequences of Permian–Triassic boundary deposits known in the area of study characterizes this sequence in full volume. In the north, the Triassic deposits are underlain by the Nedubrovo Member; in the south (the Klyazma River basin), the sections are underlain by the Vyaznikovian Horizon. The Permian–Triassic boundary adopted in the General Stratigraphic Scale of Russia for continental deposits of the East European platform (the lower boundary of the Astashikha Member) is more ancient than the one adopted in the International Stratigraphic Chart. The same geological situation is observed in the German Basin and other localities where Triassic continental deposits are developed. The ways of solving this problem are discussed in this article.     

Foraminiferal biostratigraphy and sequence stratigraphy of peritidal carbonates at the Triassic–Jurassic boundary (Karaburun Peninsula,Western Turkey)

Continuous shallow marine carbonates spanning the Triassic–Jurassic boundary are exposed in the Karaburun Peninsula, Western Turkey. The studied section (Tahtaiskele section) consists of Upper Triassic cyclic shallow marine carbonates intercalated with clastics overlain by Lower Liassic carbonates. Based on the microfacies stacking patterns, three main types of shallowing-upward cycles have been recognized. Cycles are mostly composed of subtidal facies at the bottom, intertidal/supratidal facies and/or subaerial exposure structures at the top. The duration of the cycles suggests that cycles were driven by the precessional Milankovitch rhytmicity. In the sequence stratigraphic frame of the Tahtaiskele section 4 sequence boundaries were detected and globally correlated. The first sequence boundary is located at the Alaunian–Sevatian boundary nearly coinciding with the first appearance of Triasina hantkeni. The second falls in the Rhaetian corresponding to a major sea level fall which led to the invasion of forced regressive siliciclastic deposits over the peritidal carbonates. The third occurs close to the T/J boundary and the fourth lies slightly above the base of the Jurassic. In the studied section, extinction, survival and recovery intervals have been recognized based on the stratigraphic occurrence patterns of benthic foraminifera and algae. Foraminifers became nearly totally extinct in the inner carbonate shelves at the Triassic–Jurassic boundary and an interval of approximately 0.5 my passed before the begining of the recovery of Jurassic foraminifera.     

Paleoenvironments and geochemistry across a continuous Permian–Triassic boundary section at B?kk Mountains,Hungary

The Bálvány North Permian-Triassic boundary sediments were deposited on a carbonate platform in the tropical part of the western Paleo Tethys ocean.The overall elemental geochemistry of the detailed two-metre-thick section across the boundary that we studied shows that the clastic content of the sediments came from dominantly silica-rich continental sources though with some more silica-poor inputs in the uppermost Permian and lowest Triassic limestones as shown by Ni/Al and Nb/Ta ratios.These inputs bracket, but do not coincide with, the main extinctions and associated C, O and S changes.Increased aridity at the Permian-Triassic boundary with increased wind abrasion of suitable Ti-bearing heavy minerals accounts for both the high Ti/Al and Ti/Zr ratios.Various geochemical redox proxies suggest mainly oxic depositional conditions, with episodes of anoxia, but with little systematic variation across the Permian–Triassic extinction boundary.The lack of consistent element geochemical changes across the Permian-Triassic boundary occur not only in adjacent shallower-water marine sections, and in other marine sections along the SW Tethys margin such as the Salt Range sections in Pakistan, but also in deeper shelf and oceanic sections, and in non-marine African and European continental sediments.In the absence of significant changes in physical environments, chemical changes in the atmosphere and oceans,reflected in various isotopic changes, drove the Permian–Triassic extinctions.     

The stability of palladium(II) hydroxide and hydroxy–chloride complexes: an experimental solubility study at 25–85°C and 1 bar

Solubility methods were employed to determine conditional equilibrium constants for the formation of hydroxide and mixed hydroxy–chloride complexes of Pd(II). Measurements were made over a temperature range of 25–85°C, a pH range from 0 to 12, and ionic strengths of 0.1, 0.2, 0.5 and 1.0 molal in both KCl and NaClO₄ media. Several speciation models were fit to the data using nonlinear regression, and the model yielding the best fit with the fewest number of species was accepted for each temperature and ionic strength. The conditional equilibrium constants were then fit to a function of ionic strength and temperature (including a Debye–Hückel term) to facilitate interpolation and extrapolation to infinite dilution. The following species were found to be important in KCl solutions: PdCl₄²⁻, PdCl₃(OH)²⁻, and Pd(OH)₂⁰. The relative proportions of the species are dependent on pH and ionic strength (chloride concentration). In perchlorate media the predominant species were Pd(OH)₃⁻, Pd(OH)₂⁰, PdOH⁺ and Pd²⁺, depending on pH. Conditional stability constants determined in this study agree well with those reported in previous work for the simple chloride and hydroxide complexes, but our results suggest that mixed complexes may be more important than previously thought, and that PdCl₃(OH)²⁻ may be the dominant species in seawater, followed by Pd(OH)₂⁰.     

A controversial natural border: The making of the Spanish-Portuguese boundary along the Minho River (1855–1866)

The paper intends to consider how territorial, political and legal culture dominant within mid-19th century Iberian Peninsula influenced boundary-making state practices, and to what extent a complex understanding of natural border areas -and particularly of river boundaries- emerged during this demarcation process. We draw on recent insights about, on the one hand, the important link between territory, nature and law within territorialization processes and state-making and, on the other, intrinsic problems of modern legal categories and juridical practices concerning river boundaries which are argued to be part of territorial ideologies associated with modern states.Within this framework, the paper initially addresses main practices and discourses about territory in this particular Iberian context, regarding both the enduring relevance of theory of natural boundaries within European history of modern state-making and legal codification of river boundaries delimitation by Spanish and Portuguese law internationalists. The following part of the paper presents main historical problems and territorial border disputes along the Minho River which the 1864 Spanish-Portuguese Boundary Treaty attempted to settle. Discussions and negotiations taking place within the Joint Boundary Commissions in charge of examining, delimiting and demarcating this stretch of the border are analysed as to consider how diverging interest and competing discourses about this fluvial space were displayed and related eventually to the solutions adopted by the Boundary Treaty. In that sense, state-driven boundary-making proved to be an important tool for territorial management of this border space.