Environmental hazards of arsenic associated with black shales: a review on geochemistry, enrichment and leaching mechanism

Black shales are high organic matter-rich dark coloured mudstones those are often deposited during ??oceanic anoxia events??. Most of the black shale horizons are rich in arsenic far above their average crustal abundance and are susceptible to weathering eventually leaching high As contents to the surrounding environment causing As enrichment in soil and water which adversely affect the living beings. Numerous arsenic contaminations are being reported from black shale hosted areas globally, hence, making extremely crucial to understand the processes of enrichment, leaching and broader prospective of environmental hazards. Few studies have shown arsenic concentrations as high as 6,000?mg/kg within black shales causing groundwater enrichment up to hundreds mg/L. Arsenic is commonly attached to sulphide mineral structure and partly to organic matter and clay contents during deposition and diagenetic processes. Majority of sulphide bound arsenic becomes available to oxidative dissolution processes in presence of atmospheric oxygen and water which is further triggered by certain microbial community such as Acidophilus ferrooxidans hence, enhancing arsenic release. Physical weathering processes carry the arsenic-rich shale constituents to the depositional site where it is dissolved subsequently. Chemical diffusion and mechanical transport are two prime processes transporting arsenic from black shale horizons to the water bodies or soil columns, while air pollutions are caused by combustions of organic matter-rich coaly shales.     

Discovery of agglutinated benthic foraminifera in Devonian black shales and their relevance for the redox state of ancient seas

Agglutinated foraminifera are benthic organisms that occur in marginal marine to bathyal environments. Though some taxa can live in oxygen deficient environments, they require at least some oxygen in order to persist at the seafloor. The discovery that they occur widely in Late Devonian black shales has a bearing on the boundary conditions required for episodes of extensive carbon sequestration in marine sediments and their connection to atmospheric composition and global climate. Devonian black shales of the eastern US have been studied extensively to determine the fundamental controls on carbon burial, and a range of mechanisms has been proposed. Finding agglutinated benthic foraminifera in these black shales refocuses the debate about their origin and points to limitations of earlier models.     

Palaeoenvironmental reconstruction of Lower Toarcian epicontinental black shales (Posidonia Shale, SW Germany): global versus regional control

A detailed multidisciplinary investigation (sedimentology, palaeoecology, geochemistry) of the Lower Toarcian Posidonia Shale revealed that the depositional environment was mainly controlled by sea level changes and palaeoclimate. Carbon isotope values of both, carbonates and organic matter are closely related to environmental conditions. Highly unfavourable living conditions for benthic fauna prevailed during a relative sea level low stand resulting in an enclosed stagnant basin environment. Long-term benthic colonization could not occur until water circulation improved during sea level high stand. The carbon isotope record of the Posidonia Shale is primarily controlled by redox conditions. Due to the dependency of the isotopic composition on regional palaeoecological, sedimentological and geochemical conditions, on oxygen availability and sea level changes, there is no need to infer global atmospheric changes of pCO₂ or oceanwide anoxic events.     

Berriasian–Aptian black shales of the Maiolica formation (Lombardian Basin, Southern Alps, Northern Italy): local to global events

The Lower Cretaceous Maiolica Formation represents the classic pelagic succession of the Apulian margin of the Tethys Ocean, in the Southern Alps. It consists of white calcilutites with minor marly layers and black shales. A multidisciplinary study including lithostratigraphy, nannofossil assemblage composition and organic geochemistry was performed on two composite sections in order to characterise the marl–shale layers that record production and storage of organic matter (OM) and terrigenous input in the Berriasian–Aptian interval. Such layers are associated with turbidite deposition and bottom current activity in the Late Berriasian–earliest Valanginian, Late Valanginian and Early Aptian. The uppermost Hauterivian–Barremian black shales alternate with pelagic calcilutites, forming an interval barren of redeposited layers. The quantity of organic carbon increases from the Berriasian to the Barremian; the background composition of the kerogen is continental-dominated, with varying proportions of marine-derived OM. Preservation of OM did not necessarily occur under anoxic conditions; on the contrary, storage of OM probably resulted from enhanced terrestrial input of nutrients, siliciclastics, woody and herbaceous fragments, inducing mesotrophic conditions and increased primary productivity. Higher fertility of surface waters during the Late Valanginian and Early Aptian is reflected by distinctive decreases in abundance of oligotrophic nannoconids and increase in abundance of mesotrophic Diazomatholithus in the Valanginian. During the Barremian, the rhythmic establishment of eutrophic conditions, documented by the highest amounts of marine OM, determined high-frequency fluctuations in nannoconid abundance. The Early Aptian nannoconid crisis is interpreted as the result of a major climate change and enhanced primary productivity. Variations of calcareous nannofloras, as well as changes of lithology and OM, which we describe in the Lower Cretaceous Maiolica Formation of the Lombardian Basin, can also be recognised in coeval units from other sites of the Apulian side of the Tethys. Similar episodes of siliciclastic and terrestrial OM accumulation and major changes in calcareous nannofossils are also recorded in the Upper Valanginian and Lower Aptian pelagic sediments of the Tethys, Atlantic and, partly, Pacific oceans. Such nannofossil variations are coeval with positive excursions of the δ¹³C curve and suggest perturbations of the bio-geochemical cycles at a global scale. Additional minor changes in siliciclastic and terrestrial OM accumulation as well as in nannofloras are probably the result of local events, strictly related to the physiography and evolution of the Tethyan margin.     

Fungi associated with post-harvest rot of black plum (Vitex doniana) in Nigeria

Groundnut samples from 21 selected markets in the 10 regions of Ghana yielded high levels of the aflatoxigenic fungus Aspergillus flavus on half-strength potato dextrose agar. The fungus was associated with 31.7 and 12.8%, respectively, of all damaged and undamaged kernels assayed. Only 0.24% of total kernels assayed yielded A. parasiticus. Other fungi detected from total kernels assayed were A. niger (34%), A. candidus (1.45%), A. tamarii (3.93%), A. ochraceous (5.26%), Fusarium spp. (1.7%) Penicillium spp. (5.19%), a Mucor sp. (2.3%), a Trichoderma sp. (0.2%), Rhizopus stolonifer (12%) and certain unidentifiable fungi (11.72%). Total aflatoxin levels ranging from 5.7 to 22, 168 ppb were identified with damaged kernel samples. The mycotoxin was not detected in 50% of undamaged kernel samples tested and very low levels mostly ranging from 0.1 to 12.2 ppb were associated with the undamaged samples that tested positive for aflatoxins. In a novel in vitro microbial assay to determine the effectiveness of certain plant extracts against aflatoxin synthesis, extracts from Xylopia aethiopica, Monodera myristica, Cinnamomum verum and Piper nigrum permitted fungal growth in 1.5% potato-dextrose broth while completely suppressing NOR formation. These extracts, however, could not suppress NOR formation in a yeast extract sucrose medium.     

Origin, sequence stratigraphy and depositional environment of an upper Ordovician (Hirnantian) deglacial black shale, Jordan

The upper Ordovician succession of Jordan was located 60°S, less than 100 km from the Hirnantian ice sheet margin. New graptolite dates indicate glaciation ended in Jordan in the late Hirnantian (persculptus Biozone). The succession records two glacial advances within the Ammar Formation and the subsequent deglaciations. Organic-rich black shales (Batra Formation) form part of the final deglacial transgressive succession that in-filled an existing low stand glacial continental shelf topography. The base of the black shale is coincident with the maximum flooding surface. During transgression, interfluves and sub-basin margins were breached and black shale deposition expanded rapidly across the region. The top of the black shales coincides with peak highstand. The “expanding puddle model” (sensu Wignall) for black shale deposition, adapted for the peri-glacial setting, provides the best explanation for this sequence of events.

We propose a hypothesis in which anoxic conditions were initiated beneath the halocline in a salinity stratified water column; a fresher surface layer resulted from ice meltwater generated during early deglaciation. During the initial stages of marine incursion, nutrients in the monimolimnion were isolated from the euphotic zone by the halocline. Increasing total organic carbon (TOC) and δ¹³C_org up section indicates the organic carbon content of the shales was controlled mainly by increasing bioproductivity in the mixolimnion (the Strakhov model). Mixolimnion nutrient levels were sustained by a continual and increasing supply of meltwater-derived nutrients, modulated by obliquity changes in high latitude insolation. Anoxia was sustained over tens to hundreds of thousands of years. The formation of black shales on the north Gondwana shelf was little different to those observed in modern black shale environments, suggesting that it was the nature of the Ordovician seas that pre-disposed them to anoxia.     

Palynology: A useful tool in understanding palaeoclimatic changes through the Pliocene-Pleistocene from the deep offshore Niger Delta,Nigeria

Recent global ecological problems have necessitated more research into past environments so that accurate comparisons between past and present climatic conditions can be established and projections made for the future. In order to achieve this, palynological data from Well-C from the deep offshore (> 200 m) Niger Delta region were employed in an attempt to reconstruct the Late Pliocene-Pleistocene palaeoclimate. Four informal palynofloral assemblage zones (PAZ) I–IV are defined and correlated with four major cycles of alternating dry and wet climatic conditions. Within the major cycles, savanna and montane pollen assemblages became dominant in the late-Pliocene and mid-Pleistocene, while mangroves, brackishwater swamp, freshwater swamp and lowland rainforest prevailed during the early- and late-Pleistocene. The palaeoclimate of the late Pliocene and mid-Pleistocene was relatively colder and drier, with alternating relatively warmer and wetter conditions in the early and late Pleistocene, respectively. The pollen data from Well-C showed periods of climatic change during Late Pliocene-Pleistocene times, while the periods of climatic change revealed by pollen data from Lake Tilla, NE Nigeria, during Holocene times ranged from ∼2.0 to ∼3.8 Ka. Therefore, the cyclicity of climate change during Upper Pliocene-Pleistocene time is far greater than that of Holocene times. Our palaeo-climatic reconstruction conflicts with those that indicate predominantly dry climatic conditions in the Niger Delta region during the Pliocene-Pleistocene. The reconstructed palaeoclimate in this study can help to compare the past climatic conditions to that of the present and perhaps serve as a basis for studies of future climatic change.     

Adaptation of the black tiger shrimp, Penaeus monodon, to different salinities through an excretory function of the antennal gland

Black tiger shrimps (Penaeus monodon) are able to survive and can be reared under various salinities, possibly by the cellular adaptation of their excretory system, particularly the antennal gland, which is known to regulate body fluid in crustaceans. We have investigated the morphological and biochemical alterations of the antennal glands in shrimp reared in 7, 15, or 30 ppt seawater. Drastic changes occur in animals reared under 7 ppt conditions. Ultrastructural studies of the antennal gland in shrimps reared in 7 ppt seawater have revealed that podocytic cells in the coelomosacs ramify with more cytoplasmic processes forming the filtration slits, and that the tubular labyrinth cells possess more mitochondria in their basal striation and a wider tubular lumen than those found in the other groups. Many apical cytoplasmic blebs from labyrinth cells have also been seen in the lumen of the labyrinths under 7 ppt conditions, a feature that is not as prominent under the other conditions. The expression and activity of the Na⁺/K⁺-ATPase in the antennal gland are also correlated with the surrounding environment: the lower the salinity, the higher the expression and activity of the enzyme. Immunohistochemistry results have demonstrated the highest staining intensity in the labyrinth cells of shrimps reared under 7 ppt conditions. Our findings thus suggest that one of the adaptation mechanisms of this shrimp to the surrounding salinity is the regulation of Na⁺/K⁺-ATPase expression in the antennal gland, in conjunction with subcellular changes in its excretory cells.     

Mutational Robustness Accelerates the Origin of Novel RNA Phenotypes through Phenotypic Plasticity

Novel phenotypes can originate either through mutations in existing genotypes or through phenotypic plasticity, the ability of one genotype to form multiple phenotypes. From molecules to organisms, plasticity is a ubiquitous feature of life, and a potential source of exaptations, adaptive traits that originated for nonadaptive reasons. Another ubiquitous feature is robustness to mutations, although it is unknown whether such robustness helps or hinders the origin of new phenotypes through plasticity. RNA is ideal to address this question, because it shows extensive plasticity in its secondary structure phenotypes, a consequence of their continual folding and unfolding, and these phenotypes have important biological functions. Moreover, RNA is to some extent robust to mutations. This robustness structures RNA genotype space into myriad connected networks of genotypes with the same phenotype, and it influences the dynamics of evolving populations on a genotype network. In this study I show that both effects help accelerate the exploration of novel phenotypes through plasticity. My observations are based on many RNA molecules sampled at random from RNA sequence space, and on 30 biological RNA molecules. They are thus not only a generic feature of RNA sequence space but are relevant for the molecular evolution of biological RNA.     

Mutational Robustness Accelerates the Origin of Novel RNA Phenotypes through Phenotypic Plasticity

Novel phenotypes can originate either through mutations in existing genotypes or through phenotypic plasticity, the ability of one genotype to form multiple phenotypes. From molecules to organisms, plasticity is a ubiquitous feature of life, and a potential source of exaptations, adaptive traits that originated for nonadaptive reasons. Another ubiquitous feature is robustness to mutations, although it is unknown whether such robustness helps or hinders the origin of new phenotypes through plasticity. RNA is ideal to address this question, because it shows extensive plasticity in its secondary structure phenotypes, a consequence of their continual folding and unfolding, and these phenotypes have important biological functions. Moreover, RNA is to some extent robust to mutations. This robustness structures RNA genotype space into myriad connected networks of genotypes with the same phenotype, and it influences the dynamics of evolving populations on a genotype network. In this study I show that both effects help accelerate the exploration of novel phenotypes through plasticity. My observations are based on many RNA molecules sampled at random from RNA sequence space, and on 30 biological RNA molecules. They are thus not only a generic feature of RNA sequence space but are relevant for the molecular evolution of biological RNA.     

Migration, Education, and the Status of Women in Southern Nigeria

This article examines changes in the status of women migrants, educated and noneducated, to various urban centers in one Nigerian ethnic group. The migrants are examined in contrast to women who remained residents in the rural home community. The major focus is on male-female relations in the household. Findings indicate an erosion of the private status or domestic power of educated urban women, living in monogamous, nuclear family households.     

Ecology of the Ogun River estuary,Nigeria

The distribution of benthonic communities (particularly Foraminifera) were studied from fourteen samples obtained from the Ogun River estuary and environs. Ten species of benthonic Foraminifera were identified; two of these constitute over 90% of the total foraminiferal population.Two broad biofacies are recognisable, namely the upper estuarine facies of Ammobaculites and the lower estuarine facies comprising arenaceous and calcereous forms with a preponderance of Ammonia beccarii (Linnaeus).Large populations of few species occur in the lower estuary, an area of weakly saline water with marked salinity fluctuations. The upper estuary on the other hand is sparsely populated and contains tests mainly of arenaeous Foraminifera. A few species are distinctive of particular facies but some are distributed throughout the estuary. Substrate is not a causal ecological factor, because sediments are similar in physical attributes throughout the estuary. Salinity and rate of sedimentation are among the more important factors affecting the distribution of all species. The low-energy nature of the environment is established by the abundance of faecal pellets and the fragility of the tests of the arenaceous Foraminifera.     

On the phytoplankton of Awba reservoir, Ibadan, Nigeria

The physico-chemical characteristics and phytoplankton of Awba reservoir in the University of Ibadan, Nigeria, were monitored to determine the impact of eutrophication on phytoplankton composition. The principal component analysis identified three major components influencing the physicochemistry of the water, namely trace metals, dissolved oxygen and ionic composition. Comparative analysis with a previous study showed a phenomenal increase in zinc, copper and iron levels over a 10-year period. Furthermore, the ferruginous nature of the soil contributed to the high levels of iron which exceeded the World Health Organization Standards for drinking water quality. The most abundant phytoplankton species was Microcystis aeruginosa which has been implicated in toxic blooms in freshwaters. The conditions favouring cyanophyte blooms and their implications are discussed.     

Tectonostratigraphy of Middle and Upper Palaeozoic black shales from the Porto-Tomar-Ferreira do Alentejo shear zone (W Portugal): new perspectives on the Iberian Massif

Middle/late Devonian and early Carboniferous metasedimentary sequences in the northernmost region (Porto-Espinho-Tomar) of the Ossa-Morena Zone (Portuguese Iberian Variscan Massif) contain black shales of very low to low-grade metamorphism. These metasedimentary rocks form a discrete NNW-SSE structure within a major shear zone (Porto-Tomar-Ferreira do Alentejo) and remain subparallel to the observed regional major structures (folding, thrusts or overthrusts). These black shales are overhanged and then imbricated in an upper Proterozoic metamorphic substratum. A multi-disciplinary study of these metasedimentary rocks from the Espinho-Tomar region has tectonostratigraphy, palynology, organic petrology and clay mineralogy combined methods. This approach provides new insights into the tectonic evolution and geological framework of Palaeozoic basement of the Iberian Variscides. Palaeoenvironmental and tectonostratigraphic implications on the Iberian geodynamic framework are discussed.