Cooked starchy food in hearths ca. 120 kya and 65 kya (MIS 5e and MIS 4) from Klasies River Cave, South Africa.

Plant carbohydrates currently constitute 55-80% of the modern human diet (FAO and WHO, 1997) and some of today's key global health issues are associated with excessive carbohydrate consumption. However, starch carbohydrate is still a poorly understood element of modern human diet and our past starch diet may provide insights for future research. Despite an archaeological narrative that links our early hominin ancestors to a diet that is rich in roots and tubers, there is little deep time archaeological evidence of human plant starch consumption. Geneticists hypothesise that the duplication of starch digestion genes in early Homo sapiens (∼300 kya), is an adaptive response to an increased starch diet. Here we offer the earliest evidence of identified fragments of charred starch plant tissue (parenchyma) from cave and rock shelter hearths dated to Marine Isotope Stage (MIS) 5e and MIS 4, from the Middle Stone Age (MSA) site of Klasies River main site, South Africa (34.06°S, 24.24°E).

The depositional environments of Schöningen 13 II-4 and their archaeological implications.

Geoarchaeological research at the Middle Pleistocene site of Schöningen 13 II-4, often referred to as the Speerhorizont, has focused on describing and evaluating the depositional contexts of the well-known wooden spears, butchered horses, and stone tools. These finds were recovered from the transitional contact between a lacustrine marl and an overlying organic mud, originally thought to be a peat that accumulated in place under variable moisture conditions. The original excavators proposed that hominin activity, including hunting and butchery, occurred on a dry lake shore and was followed by a rapid sedimentation of organic deposits that embedded and preserved the artifacts. Our geoarchaeological analysis challenges this model. Here, we present evidence that the sediments of Schöningen 13 II-4 were deposited in a constantly submerged area of a paleolake. Although we cannot exclude the possibility that the artifacts were deposited during a short, extreme drying event, there are no sedimentary features indicative of surface exposure in the sediments. Accordingly, this paper explores three main alternative models of site formation: anthropogenic disposal of materials into the lake, a geological relocation of the artifacts, and hunting or caching on lake-ice. These models have different behavioral ramifications concerning hominin knowledge and exploitation of the landscape and their subsistence strategies.

On the evidence for human use and control of fire at Schöningen.

When and how humans began to control fire has been a central debate in Paleolithic archaeology for decades. Fire plays an important role in technology, social organization, subsistence, and manipulation of the environment and is widely seen as a necessary adaptation for the colonization of northern latitudes. Many researchers view purported hearths, burnt wooden implements, and heated flints from Schöningen as providing the best evidence for the control of fire in the Lower Paleolithic of Northern Europe. Here we present results of a multianalytical study of the purported hearths along with a critical examination of other possible evidence of human use or control of fire at Schöningen. We conclude that the analyzed features and artifacts present no convincing evidence for human use or control of fire. Our study also shows that a multianalytical, micro-contextual approach is the best methodology for evaluating claims of early evidence of human-controlled fire. We advise caution with macroscopic, qualitative identification of combustion features, burnt flint, and burnt wood without the application of such techniques as micromorphology, Fourier transform infrared (FTIR) spectroscopy, organic petrology, luminescence, and analysis of mineral magnetic parameters. The lack of evidence for the human control of fire at Schöningen raises the possibility that fire control was not a necessary adaptation for the human settlement of northern latitudes in the Lower Paleolithic.

A previously undescribed organic residue sheds light on heat treatment in the Middle Stone Age.

South Africa has in recent years gained increasing importance for our understanding of the evolution of 'modern human behaviour' during the Middle Stone Age (MSA). A key element in the suite of behaviours linked with modern humans is heat treatment of materials such as ochre for ritual purposes and stone prior to tool production. Until now, there has been no direct archaeological evidence for the exact procedure used in the heat treatment of silcrete. Through the analysis of heat-treated artefacts from the Howiesons Poort of Diepkloof Rock Shelter, we identified a hitherto unknown type of organic residue - a tempering-residue - that sheds light on the processes used for heat treatment in the MSA. This black film on the silcrete surface is an organic tar that contains microscopic fragments of charcoal and formed as a residue during the direct contact of the artefacts with hot embers of green wood. Our results suggest that heat treatment of silcrete was conducted directly using an open fire, similar to those likely used for cooking. These findings add to the discussion about the complexity of MSA behaviour and appear to contradict previous studies that had suggested that heat treatment of silcrete was a complex (i.e., requiring a large number of steps for its realization) and resource-consuming procedure.

Middle and Upper Paleolithic occupations of Fumane Cave (Italy): a geoarchaeological investigation of the anthropogenic features.

Here we present the results of a microcontextual analysis of purported combustion features recovered from Middle and Upper Paleolithic occupations at the cave site of Fumane, Italy. Our analyses, which integrate micromorphology with organic petrology, show that only a few of the features represent primary, intact hearths; some of them show evidence for various phases of anthropogenic reworking, either through trampling or sweeping and dumping. Several of the features are multi-layered and reflect a complex formation history of various activities related to combustion and site maintenance. Many appear to be the remnants of occupation horizons only partially preserved and peripherally related to combustion. Within several of the intact hearths from the Mousterian, we were able to identify variable fuel sources in different features, implying a degree of flexibility in the fuel-selection strategies of the Neanderthal occupants of Fumane. In this study we design a classification system of the anthropogenic features and also conduct a spatial analysis, through which we can infer diachronic patterns in the frequency and intensity of site occupation and the spatial distribution of activities. We note a decrease in frequency of combustion features throughout the Mousterian which continues into the Uluzzian. The features associated with the Protoaurignacian occupation, in contrast with those from the Mousterian, are multi-layered and well-defined. We argue that these trends, which correspond with other trends in artefact frequency, imply changes in the settlement dynamics of the site during the transition from the last Neanderthal occupation of the cave to the arrival of modern humans.

High-resolution sediment analysis reveals Middle Bronze Age byre-houses at the site of Oppeano (Verona province, NE Italy).

High-resolution sediment analysis allowed us to identify two Middle Bronze Age (MBA 1, 1650-1550 cal a BCE) byre-houses at the waterlogged site of Oppeano "4D", south of Verona (Veneto region, NE Italy). The site lies in a low-lying valley incised by the Adige River in its LGM alluvial fan. In this fluvio-palustrine environment burial and taphonomic conditions were such that the archaeological record was extremely well preserved. The wooden elements making up basal parts of nine 'huts' were in fact exposed at Oppeano, and so were their internal accretion deposits. These featured finely laminated dung units deriving from the stalling of small herbivores, possibly ovicaprids, intercalated with repeated accumulations of wood ash. This was produced in large and multi-stratified hearths that were exposed within each hut. Organic petrology provided evidence of the production of wood tar inside one of the studied structures. At Oppeano 4D it was thus demonstrated that these structures were not just byres or stables, but spaces that housed humans together with animals at least during some periods of the year, hence byre-houses. The identification of byre-houses in a Middle Bronze Age settlement is key for the reconstruction of socio-economic aspects of Bronze Age economy and production systems.

Enhanced sorption of PAHs in natural-fire-impacted sediments from Oriole Lake, California.

Surface sediment cores from Oriole Lake (CA) were analyzed for organic carbon (OC), black carbon (BC), and their δ(13)C isotope ratios. Sediments displayed high OC (20-25%) and increasing BC concentrations from ∼0.40% (in 1800 C.E.) to ∼0.60% dry weight (in 2000 C.E.). Petrographic analysis confirmed the presence of fire-derived carbonaceous particles/BC at ∼2% of total OC. Natural fires were the most likely cause of both elevated polycyclic aromatic hydrocarbon (PAH) concentrations and enhanced sorption in Oriole Lake sediments prior to 1850, consistent with their tree-ring-based fire history. In contrast to other PAHs, retene and perylene displayed decreasing concentrations during periods with natural fires, questioning their use as fire tracers. The occurrence of natural fires, however, did not result in elevated concentrations of black carbon or chars in the sediments. Only the 1912-2007 sediment layer contained anthropogenic particles, such as soot BC. In this layer, combining OC absorption with adsorption to soot BC (using a Freundlich coefficient n = 0.7) explained the observed sorption well. In the older layers, n needed to be 0.3 and 0.5 to explain the enhanced sorption to the sediments, indicating the importance of natural chars/inertinites in sorbing PAHs. For phenanthrene, values of n differed significantly between sorption to natural chars (0.1-0.4) and sorption to anthropogenic black carbon (>0.5), suggesting it could serve as an in situ probe of sorbents.

Occurrence of coal and coal-derived particle-bound polycyclic aromatic hydrocarbons (PAHs) in a river floodplain soil.

A PAH contaminated river floodplain soil was separated according to grain size and density. Coal and coal-derived particles from coal mining, coal industry and coal transportation activities were identified by organic petrographic analysis in our samples. Distinct concentrations of PAHs were found in different grain size and density fractions, however, similar distribution patterns of PAHs indicated similar sources. In addition, although light fractions had the mass fraction by weight of less than 5%, they contributed almost 75% of the total PAHs in the soil. PAH concentrations of all sub fractions showed positive correlation with their TOC contents. Altogether, coal and coal-derived particles that were abundant in light fractions could be the dominant geosorbents for PAHs in our samples.

Identification of carbonaceous geosorbents for PAHs by organic petrography in river floodplain soils.

Organic petrographic analysis was applied to provide direct information on carbonaceous geosorbents for PAHs in river floodplain soils. The anthropogenic OM group (primarily coal and coal-derived particles) displayed large volume amounts for all the soil samples. Distinct PAH concentrations with similar PAH distribution patterns were determined in grain size and density fractions for each sample. Two-ring PAHs had stronger correlation to organic carbon (OC) than black carbon (BC) contents, while heavier PAHs showed correlation to BC, rather than OC. In this study, we combined grain size and density separation, PAH determinations, TOC and BC measurements, and organic petrographic identification, and concluded that two-ring PAHs in soils were associated to coal particles. Other heavier PAHs could be more controlled by black carbon (BC), which were mostly coal-derived particles from former coal mining and coal industrial activity.

Accumulation of polycyclic aromatic hydrocarbons in rural soils based on mass balances at the catchment scale.

Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic organic pollutants that are ubiquitously distributed in the environment at relatively high concentrations. In our study we investigated the long-term fate of atmospheric PAHs in soils of rural areas, resulting from diffuse pollution based on mass balances at the catchment scale. By determining PAHs in several environmental compartments, estimates of soil storages and water fluxes were made and compared with atmospheric deposition. The results indicate that more than 90% of the incoming PAHs remain in the catchments and accumulate in the topsoils. Furthermore, revolatilization of PAHs from soils and degradation in the soils is very limited, resulting in ongoing accumulation in topsoils, in particular for low-volatile PAHs. Combustion-derived carbonaceous particles were detected in atmospheric deposition as well as in the soil samples. Since these particles are very strong adsorbents, they are suspected to play a key role in the environmental fate of the diffuse distributed PAHs.

Heterogeneous carbonaceous matter in sedimentary rock lithocomponents causes significant trichloroethylene (TCE) sorption in a low organic carbon content aquifer/aquitard system.

This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on trichloroethylene (TCE) sorption for a low fraction organic carbon content (foc) alluvial sedimentary aquifer and aquitard system (foc=0.046-0.105%). The equilibrium TCE sorption isotherms were highly nonlinear with Freundlich exponents of 0.46-0.58. Kerogen+black carbon was the dominant CM fraction extracted from the sediments and accounted for >60% and 99% of the total in the sands and silt, respectively. Organic petrological examination determined that the kerogen included abundant amorphous organic matter (bituminite), likely of marine origin. The dark calcareous siltstone exhibited the greatest TCE sorption among aquifer lithocomponents and accounted for most sorption in the aquifer. The results suggest that the source of the thermally altered CM, which causes nonlinear sorption, was derived from parent Paleozoic marine carbonate rocks that outcrop throughout much of New York State. A synthetic aquifer-aquitard unit system (10% aquitard) was used to illustrate the effect of the observed nonlinear sorption on mass storage potential at equilibrium. The calculation showed that >80% of TCE mass contained in the aquifer was sorbed on the aquifer sediment at aqueous concentration <1000 µgL(-1). These results show that sorption is likely a significant contributor to the persistence of a TCE groundwater plume in the aquifer studied. It is implied that sorption may similarly contribute to TCE persistence in other glacial alluvial aquifers with similar geologic characteristics, i.e., comprised of sedimentary rock lithocomponents that contain thermally altered CM.

Influence of coal-tar sealcoat and other carbonaceous materials on polycyclic aromatic hydrocarbon loading in an urban watershed.

Carbonaceous material (CM) particles are the principal vectors transporting polycyclic aromatic hydrocarbons (PAHs) into urban waters via runoff; however, characteristics of CM particles in urban watersheds and their relative contributions to PAH contamination remain unclear. Our objectives were to identify the sources and distribution of CM particles in an urban watershed and to determine the types of CMs that were the dominant sources of PAHs in the lake and stream sediments. Samples of soils, parking lot and street dust, and streambed and lake sediment were collected from the Lake Como watershed in Fort Worth, Texas. Characteristics of CM particles determined by organic petrography and a significant correlation between PAH concentrations and organic carbon in coal tar, asphalt, and soot indicate that these three CM particle types are the major sources and carriers of PAHs in the watershed. Estimates of the distribution of PAHs in CM particles indicate that coal-tar pitch, used in some pavement sealcoats, is a dominant source of PAHs in the watershed, and contributes as much as 99% of the PAHs in sealed parking lot dust, 92% in unsealed parking lot dust, 88% in commercial area soil, 71% in streambed sediment, and 84% in surficial lake sediment.

The role of condensed carbonaceous materials on the sorption of hydrophobic organic contaminants in subsurface sediments.

The identification and characterization of carbonaceous materials (CMs) that control hydrophobic organic chemical (HOC) sorption is essential to predict the fate and transport of HOCs in soils and sediments. The objectives of this paper are to determine the types of CMs that control HOC sorption in the oxidized and reduced zones of a glacially deposited groundwater sediment in central Illinois, with a special emphasis on the roles of kerogen and black carbon. After collection, the sediments were treated to obtain fractions of the sediment samples enriched in different types of CMs (e.g., humic acid, kerogen, black carbon), and selected fractions were subject to quantitative petrographic analysis. The original sediments and their enrichment fractions were evaluated for their ability to sorb trichloroethene (TCE), a common groundwater pollutant. Isotherm results and mass fractions of CM enrichments were used to calculate sorption contributions of different CMs. The results indicate that CMs in the heavy fractions dominate sorption because of their greater mass. Black carbon mass fractions of total CMs in the reduced sediments were calculated and used to estimate the sorption contribution of these materials. Results indicate that in the reduced sediments, black carbon may sequester as much as 32% of the sorbed TCE mass, butthat kerogen and humin are the dominant sorption environments. Organic carbon normalized sorption coefficients (K(oc)) were compared to literature values. Values for the central Illinois sediments are relatively large and in the range of values determined for materials high in kerogen and humin. This work demonstrates the advantage of using both sequential chemical treatment and petrographic analysis to analyze the sorption contributions of different CMs in natural soils and sediments, and the importance of sorption to natural geopolymers in groundwater sediments not impacted by anthropogenic sources of black carbon.