Dermal absorption of high molecular weight parent and alkylated polycyclic aromatic hydrocarbons from manufactured gas plant soils using in vitro assessment.

An enhanced in vitro human dermal bioavailability method was developed to measure the release of twenty parent and seven alkylated high molecular weight (HMW) polycyclic aromatic hydrocarbons (PAHs) from contaminated soils collected from five former manufactured Gas Plants (MGP) in England. GC-MS/MS was used to quantify HMW PAHs in soil, Strat-M artificial membrane representing skin, and synthetic receptor solution (RS) representing systemic circulation at 1-h, 10-h, and 24-h timesteps. Fluoranthene and pyrene exhibited the highest fluxes from soils to membrane (ranging from 9.5 - 281 ng/cm2/h) and soil to RS (

Characterisation of former manufactured gas plant soils using parent and alkylated polycyclic aromatic hydrocarbons and Rock-Eval(6) pyrolysis.

Soils sampled from 10 former manufactured gas plants (MGP) in the UK were investigated using gas chromatography mass spectrometry (GC-MS/MS) and Rock-Eval (6) Pyrolysis (RE). RE is a screening tool used to characterise bulk organic matter in soils via the release of carbon compounds during pyrolysis and oxidation. Both the distributions and concentrations of 30 parent and 21 alkylated polycyclic aromatic hydrocarbons (PAHs) and the parameters of RE were analysed to establish relationships between soils and the MGP processes history. Principal component analysis (PCA) using the PAHs distributions and RE parameters can assist with differentiating between MGP processes. MGP processes utilizing oil provided the clearest results, attributed to petrogenic signatures with high proportions of low molecular weight PAHs. Processes using lower temperature processes were distinguished by higher proportions of high molecular weight PAHs. RE parameters alone were unable to distinguish MGP processes but showed potential in estimating the lability and thus the amount of PAH that could be released from soils. This research provides new insights that may be useful in understanding and characterising the risks posed to human health from PAHs in soils.

X-ray computed tomography: A novel non-invasive approach for the detection of microplastics in sediments?

As a non-invasive imaging technique, this study explores the application of Computed Tomography (CT) in microplastics research, assessing its potential to distinguish different types and sizes of microplastics (polypropylene, polyethylene terephthalate, polyethylene, and polyvinyl chloride) from homogenised river-estuarine sediment. When examined in layers within artificial cores, all microplastic types could be observed by CT imagery, with good contrast in X-ray attenuation (based on image gray level intensity) against background sediments. Large microplastics (4 mm diameter) were also detectable when distributed randomly amongst the sediment. These spiked cores had sufficient difference in attenuation to allow segmentation between type, and therefore isolate individual microplastics. Due to limitations on scan resolution, smaller microplastics (≤125 µm diameter) could not be detected in spiked cores. Scans of two sediment cores from a Thames River tributary (UK) revealed two distinctive sediment structures which could influence microplastic accumulation. This information would be lost using conventional recovery procedures.

Detecting tropical peatland degradation: Combining remote sensing and organic geochemistry.

Tropical peatlands are important carbon stores that are vulnerable to drainage and conversion to agriculture. Protection and restoration of peatlands are increasingly recognised as key nature based solutions that can be implemented as part of climate change mitigation. Identification of peatland areas that are important for protection and restauration with regards to the state of their carbon stocks, are therefore vital for policy makers. In this paper we combined organic geochemical analysis by Rock-Eval (6) pyrolysis of peat collected from sites with different land management history and optical remote sensing products to assess if remotely sensed data could be used to predict peat conditions and carbon storage. The study used the North Selangor Peat Swamp forest, Malaysia, as the model system. Across the sampling sites the carbon stocks in the below ground peat was ca 12 times higher than the forest (median carbon stock held in ground vegetation 114.70 Mg ha-1 and peat soil 1401.51 Mg ha-1). Peat core sub-samples and litter collected from Fire Affected, Disturbed Forest, and Managed Recovery locations (i.e. disturbed sites) had different decomposition profiles than Central Forest sites. The Rock-Eval pyrolysis of the upper peat profiles showed that surface peat layers at Fire Affected, Disturbed Forest, and Managed Recovery locations had lower immature organic matter index (I-index) values (average I-index range in upper section 0.15 to -0.06) and higher refractory organic matter index (R -index) (average R-index range in upper section 0.51 to 0.65) compared to Central Forest sites indicating enhanced decomposition of the surface peat. In the top 50 cm section of the peat profile, carbon stocks were negatively related to the normalised burns ratio (NBR) (a satellite derived parameter) (Spearman's rho = -0.664, S = 366, p-value = <0.05) while there was a positive relationship between the hydrogen index and the normalised burns ratio profile (Spearman's rho = 0.7, S = 66, p-value = <0.05) suggesting that this remotely sensed product is able to detect degradation of peat in the upper peat profile. We conclude that the NBR can be used to identify degraded peatland areas and to support identification of areas for conversation and restoration.

Hydroclimatic vulnerability of peat carbon in the central Congo Basin.

The forested swamps of the central Congo Basin store approximately 30 billion metric tonnes of carbon in peat1,2. Little is known about the vulnerability of these carbon stocks. Here we investigate this vulnerability using peat cores from a large interfluvial basin in the Republic of the Congo and palaeoenvironmental methods. We find that peat accumulation began at least at 17,500 calibrated years before present (cal. yr BP; taken as AD 1950). Our data show that the peat that accumulated between around 7,500 to around 2,000 cal. yr BP is much more decomposed compared with older and younger peat. Hydrogen isotopes of plant waxes indicate a drying trend, starting at approximately 5,000 cal. yr BP and culminating at approximately 2,000 cal. yr BP, coeval with a decline in dominant swamp forest taxa. The data imply that the drying climate probably resulted in a regional drop in the water table, which triggered peat decomposition, including the loss of peat carbon accumulated prior to the onset of the drier conditions. After approximately 2,000 cal. yr BP, our data show that the drying trend ceased, hydrologic conditions stabilized and peat accumulation resumed. This reversible accumulation-loss-accumulation pattern is consistent with other peat cores across the region, indicating that the carbon stocks of the central Congo peatlands may lie close to a climatically driven drought threshold. Further research should quantify the combination of peatland threshold behaviour and droughts driven by anthropogenic carbon emissions that may trigger this positive carbon cycle feedback in the Earth system.

Contrasting sewage, emerging and persistent organic pollutants in sediment cores from the River Thames estuary, London, England, UK.

Sedimentary organic pollution in the urban reaches of the Thames estuary is changing from fossil fuel hydrocarbons to emerging synthetic chemicals. De-industrialisation of London was assessed in three cores from Chiswick (Ait/Eyot) mud island using pharmaceuticals, faecal sterols, hydrocarbons (TPH, PAH), Black Carbon (BC) and organotins (TBT). These ranked in the order; BC 7590-30219 mg/kg, mean 16,000 mg/kg > TPH 770-4301, mean 1316 mg/kg > Σ16PAH 6.93-107.64, mean 36.46 mg/kg > coprostanol 0.0091-0.42 mg/kg, mean of 0.146 mg/kg > pharmaceuticals 2.4-84.8 µg/kg, mean 25 µg/kg. Hydrocarbons co-varied down-profile revealing rise (1940s), peak (1950s -1960s) and fall (1980s) and an overall 3 to 25-fold decrease. In contrast, antibiotics, anti-inflammatory (ibuprofen, paracetamol) and hormone (17ß-estradiol) increased 3 to 50-fold toward surface paralleling increasing use (1970s-2018). The anti-epileptics, carbamazepine and epoxcarbamazepine showed appreciable down-core mobility. Faecal sterols confirmed non-systematic incorporation of treated sewage. Comparison to UK sediment quality guidelines indicate exceedance of AL2 for PAH whereas TBT was below AL1.

Kerogen nanoscale structure and CO2 adsorption in shale micropores.

Gas storage and recovery processes in shales critically depend on nano-scale porosity and chemical composition, but information about the nanoscale pore geometry and connectivity of kerogen, insoluble organic shale matter, is largely unavailable. Using adsorption microcalorimetry, we show that once strong adsorption sites within nanoscale network are taken, gas adsorption even at very low pressure is governed by pore width rather than chemical composition. A combination of focused ion beam with scanning electron microscopy and transmission electron microscopy reveal the nanoscale structure of kerogen includes not only the ubiquitous amorphous phase but also highly graphitized sheets, fiber- and onion-like structures creating nanoscale voids accessible for gas sorption. Nanoscale structures bridge the current gap between molecular size and macropore scale in existing models for kerogen, thus allowing accurate prediction of gas sorption, storage and diffusion properties in shales.

Ambrein: a minor, but common constituent of mammalian faeces?

For nearly 200 years, the only natural source of the alcohol ambrein has been coproliths produced in about 1% of sperm whales and in related jetsam. However, the finding of ambrein in adipocere/faeces of human corpses, led us to hypothesise that ambrein might occur in the faeces of other mammals. Herein, we used a recently developed gas chromatography-mass spectrometry method, with suitable derivatisation of the hindered hydroxy group of ambrein, to screen a number of extracts of mammalian faeces. Minor proportions of ambrein were detected in digested human sewage sludge and in the dung of elephant, domestic cattle, giraffe and buffalo. Whether ambrein formation in the terrestrial species is associated with coprolith formation, is unknown, but solid deposits known as enteroliths and fecaliths occur in humans and some domestic animals.

Grain size and organic carbon controls polyaromatic hydrocarbons (PAH), mercury (Hg) and toxicity of surface sediments in the River Conwy Estuary, Wales, UK.

The Conwy estuary was evaluated for sediment quality. Microtox bioassay revealed 38 of 39 sites were non-toxic. Hg ranged from 0.001 to 0.153 µg kg-1, mean 0.026 mg kg-1, Σ16 PAH from 18 to 1578 µg kg-1, mean 269 µg kg-1, Σ22 PAH, 18 to 1871 µg kg-1 mean to 312 µg kg-1, two sites had high perylene relative to ΣPAH. Σ22PAH correlated positively with TOC, clay and silt (R2 0.89, 0.92, 0.90) and negatively with sand. Multivariate statistics, delineated four spatial (site) and five variable (measurements) clusters. Spatial clustering relates to sediment grain size, in response to hydrodynamic processes in estuary; fine (clay to silt) sized sediments exhibit the highest Hg and PAH content, because these components partitioned into the fine fraction. Comparison to national and international environmental standards suggests Hg and PAH content of Conwy sediments are unlikely to harm ecology or transfer up into the human food chain.

Organic pollutants, heavy metals and toxicity in oil spill impacted salt marsh sediment cores, Staten Island, New York City, USA.

Sediment cores from Staten Island's salt marsh contain multiple historical oil spill events that impact ecological health. Microtox solid phase bioassay indicated moderate to high toxicity. Multiple spikes of TPH (6524 to 9586 mg/kg) and Σ16 PAH (15.5 to 18.9 mg/kg) were co-incident with known oil spills. A high TPH background of 400-700 mg/kg was attributed to diffuse sources. Depth-profiled metals Cu (1243 mg/kg), Zn (1814 mg/kg), Pb (1140 mg/kg), Ni (109 mg/kg), Hg (7 mg/kg), Cd 15 (mg/kg) exceeded sediment quality guidelines confirming adverse biological effects. Changes in Pb206/207 suggested three metal contaminant sources and diatom assemblages responded to two contamination events. Organic and metal contamination in Saw Mill Creek Marsh may harm sensitive biota, we recommend caution in the management of the 20-50 cm sediment interval because disturbance could lead to remobilisation of pre-existing legacy contamination into the waterway.

Trends in heavy metals, polychlorinated biphenyls and toxicity from sediment cores of the inner River Thames estuary, London, UK.

River islands (Ait or Eyot) within the inner tidal Thames serve as unique recorders of current and historical estuarine chemical pollution. Sediment cores from Chiswick Ait were assessed for contamination using Microtox® solid phase bioassay, stable isotopes (δ13C, δ15N), heavy metals and polychlorinated biphenyls (PCBs). Microtox® classified these sediments as non-toxic to moderately toxic and bulk isotopes identified a change in organic input. Metals Cu, Zn, Cr, Ni, Cd, Hg and Ag showed parallel rise, peak and fall profiles which when allied to a 207/208Pb and 137Cs based chronology supported major changes in trace metal contributions corresponding to approximate input times of 1940 (rise), 1963 (peak) and 1985 (fall). Metals ranged from Cu 15 to 373 mg kg-1 (mean 141 mg kg-1), Zn 137 to 1331 mg kg-1 (mean 576 mg kg-1), Cr 14-351 mg kg-1 (mean 156 mg kg-1), Pb 10 to 1506 mg kg-1 (mean 402 mg kg-1), As 1 to 107 (mean 38 mg kg-1), Ni 11 to 113 mg kg-1 (mean 63 mg kg-1), Cd 0.2 to 53 mg kg-1 (mean 9 mg kg-1), Hg 1 to 8 mg kg-1 (mean 4.6 mg kg-1) and Ag from 0.7 to 50 mg kg-1 (mean 7.5 mg kg-1). Down core total PCBs ranged from 10.5 to 121 µg kg-1 and mean of 39 µg kg-1. The rise, peak and fall of Cu, Zn, Cr, Ni, Cd and Ag pollution matched local sewage works' treatment discharge records. Whereas the Hg, Pb and As profiles were disconnected, reflecting alternative historic sources and or partitioning behaviour. Comparison to marine sediment quality guidelines indicate that Zn, Pb, Ni, Cd and Hg exceed action level 2, whereas sedimentary Cu, Cr and As concentrations were above action level 1 (no action) but below action level 2 (further investigation required). The river islands of the tidal Thames capture a unique contaminant chemistry record due in part to their location in the tidal frame (salinity minimum) and close proximity to west London.

Shale gas reserve evaluation by laboratory pyrolysis and gas holding capacity consistent with field data.

Exploration for shale gas occurs in onshore basins, with two approaches used to predict the maximum gas in place (GIP) in the absence of production data. The first estimates adsorbed plus free gas held within pore space, and the second measures gas yields from laboratory pyrolysis experiments on core samples. Here we show the use of sequential high-pressure water pyrolysis (HPWP) to replicate petroleum generation and expulsion in uplifted onshore basins. Compared to anhydrous pyrolysis where oil expulsion is limited, gas yields are much lower, and the gas at high maturity is dry, consistent with actual shales. Gas yields from HPWP of UK Bowland Shales are comparable with those from degassed cores, with the ca. 1% porosity sufficient to accommodate the gas generated. Extrapolating our findings to the whole Bowland Shale, the maximum GIP equate to potentially economically recoverable reserves of less than 10 years of current UK gas consumption.

Petroleomic depth profiling of Staten Island salt marsh soil: 2ω detection FTICR MS offers a new solution for the analysis of environmental contaminants.

Staten Island is located in one of the most densely populated regions of the US: the New York/New Jersey Estuary. Marine and industrial oil spills are commonplace in the area, causing the waterways and adjacent marshes to become polluted with a range of petroleum-related contaminants. Using Rock-Eval pyrolysis, the hydrocarbon impact on a salt marsh was assessed at regular intervals down to 90 cm, with several key sampling depths of interest identified for further analysis. Ultrahigh resolution data are obtained by direct infusion (DI) atmospheric pressure photoionization (APPI) on a 12 T solariX Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS) allowing trends in the compositional profile with depth to be observed, such as changes in the relative hydrocarbon intensity and the relative contributions from oxygen- and sulfur-containing groups. These trends may correlate with the timing of major oil spills and leaks of petroleum and other industrial chemicals into the waterways. The use of gas chromatography (GC) coupled to a 7 T solariX 2XR FTICR MS equipped with an atmospheric pressure chemical ionization (APCI) ion source offers retention time resolved and extensive compositional information for the complex environmental samples complementary to that obtained by DI-APPI. The compositional profile observed using GC-APCI FTICR MS includes contributions from phosphorous-containing groups, which may be indicative of contamination from other anthropogenic sources.

Legacy PBDEs and NBFRs in sediments of the tidal River Thames using liquid chromatography coupled to a high resolution accurate mass Orbitrap mass spectrometer.

Surface sediment samples (n = 45) were collected along a 110 km transect of the river Thames in October 2011, starting from Teddington Lock out through the industrial area of London to the southern North Sea. Several legacy and novel brominated flame retardants (NBFRs) were analysed, including 13 polybrominated diphenyl ethers (PBDEs) (congeners 17, 28, 47, 99, 100, 153, 154, 183, 196, 197, 206, 207 and 209), hexabromocyclododecane (HBCDDs), tetrabromobisphenol A (TBBPA), hexabromobenzene (HBB), 2,4,6-tribromophenol (TBP), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB or TBB), bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP or TBPH), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), pentabromoethylbenzene (PBEB), anti/syn-dechlorane plus (a/s-DP), 2,2',4,4',5,5'-hexabromobiphenyl (BB153) and α-,ß-1,2-dibromo-4-(1,2-dibromoethyl) cyclohexane (α-,ß-DBE-DBCH or TBECH). A novel analysis method based on liquid chromatographic separation, followed by high resolution accurate mass detection using the Orbitrap platform was used for quantification. Results revealed that BDE-209 had the highest concentrations (<0.1 to 540 µg kg-1 dw) and detection frequency, accounting for 95% of all PBDE congeners measured. Indicative evidence of debromination of the PentaBDE technical mixture was observed through elevated relative abundance of BDE-28 in sediment compared to the Penta-BDE formulation. NBFRs were detected at comparable levels to PBDEs (excluding BDE-209), which indicates increasing use of the former. Spatial trend analysis showed that samples from industrial areas had significantly higher concentrations of Σ12PBDEs, ΣHBCDDs, TBBPA, BEH-TEBP, BTBPE and TBP. Three locations showed high concentrations of HBCDDs with diastereomer patterns comparable to the technical mixture, which indicate recent input sources to the sediment.

Distribution and speciation of phosphorus in foreshore sediments of the Thames estuary, UK.

Estuarine sediments can be a source of Phosphorus (P) to coastal waters, contributing to nutrient budgets and geochemical cycles. In this work, the concentration and speciation of P in 47 cores were examined from the inter-tidal mud flats of the tidal river Thames (~120km). Results of P concentration and speciation were combined with published data relating to known sediment dynamics and water chemistry (salinity) within the estuary to produce a conceptual model of sediment-P behaviour. Results demonstrated significant P desorption occurring after sediment passed through the Estuarine Turbidity Maximum and when the salinity of the river water exceeded ~6ppt. It was found that organic P was desorbed to a greater extent than inorganic P in the lower estuary. Models were used to identify those geochemical parameters that contributed to the Total P (R2=0.80), oxalate extractable P (R2=0.80) and inorganic P (R2=0.76) concentrations within the Thames estuary.

Carbon isotope alteration during the thermal maturation of non-flowering plant species representative of those found within the geological record.

RATIONALE: The carbon isotope (δ13 C value) composition of fossil plant material is routinely used as a proxy of past climate and environment change. However, palaeoclimate interpretation requires assumptions about the stability of δ13 C values in plant material during its decomposition and incorporation into sediments. Previous work on modern angiosperm species shows δ13 C changes of several per mille during simulated decomposition experiments. However, no such tests have been undertaken on non-flowering plants, which are found extensively within the geological record. These plants have distinctly different cellulose-to-lignin ratios from those of their angiosperm counterparts, potentially creating hitherto unknown variations in the original to fossil δ13 C signatures. METHODS: To test the extent of δ13 C change during decomposition we have subjected a number of plants, representing more basal, non-flowering plant lineages (cycads, ferns, horsetails and dawn redwood), to artificial decay using a hydrothermal maturation technique at two temperatures over periods of up to 273 hours. Subsamples were extracted every 12-16 hours and analysed for their δ13 C and %C values using a Carlo Erba 1500 elemental analyser, and VG TripleTrap and Optima mass spectrometers. RESULTS: The %C values increased for all samples through the maturation process at both temperatures with the largest increases observed within the first 24 hours. Decreases in δ13 C values were observed for all plants at 300°C and for two of the species at the lower temperature (200°C). The maximum shift in the δ13 C value related to experimental decomposition was -0.90‰ (horsetail), indicating a preferential loss of 13 C during thermal maturation. CONCLUSIONS: The reduction in the δ13 C value potentially suggests a preferential loss of isotopically heavier cellulose in relation to the isotopically lighter lignin component during maturation. The isotopic offset observed here (<0.9‰) means that palaeoclimatic interpretation of δ13 C values from non-flowering plant material within the geological record remains robust, but only where interpretations are based on variations in δ13 C values greater than 1‰. Copyright © 2016 John Wiley & Sons, Ltd.

Effects of drying and comminution type on the quantification of Polycyclic Aromatic Hydrocarbons (PAH) in a homogenised gasworks soil and the implications for human health risk assessment.

This research investigates the effect of nine physical treatment types comprising a serial combination of three drying (air, freeze and oven) and two comminution (milling and sieving) methods on the quantification of PAH in a soil sample from a former gasworks. Results show that treatment type has a significant effect on PAH concentration (p⩽0.05). Naphthalene, 1-methylnaphthalene and 2-methylnaphthalene concentrations were significantly higher for air drying and freeze drying treatments than for oven drying. It is suggested that naphthalene and similarly volatile PAH losses were greater for oven drying due to the application of fanned warm air which is thought to cause volatilisation. Analytical precision was significantly improved for milled samples compared with sieved samples. The reason milling results in greater precision is assigned to the improved solvent extraction efficiency when natural grain size is altered due to crushing. The analytical data were compared to residential generic assessment criteria (GAC) used for risk-based land management. It was shown that the naphthalene GAC was lower than all freeze drying and air drying concentrations but was within the oven drying concentration range, illustrating that a false negative could be concluded during risk evaluation is oven dried data were used. Overall, it is recommended that air drying or freeze drying is a better choice than oven drying if the quantification of low molecular weight PAH forms an important objective of sample characterisation for risk-based land management, otherwise freeze drying and milling is recommended.

Sedimentary transport and fate of polycyclic aromatic hydrocarbons (PAH) from managed burning of moorland vegetation on a blanket peat, South Yorkshire, UK.

This study reports the concentrations of 18 polycyclic aromatic hydrocarbons (PAH) from managed burning of moorland vegetation and compares them to PAH in catchment vegetation, underlying peats, head water suspended sediment (HSS), stream water and reservoir sediment cores. Total PAH ranged from 203 to 11,112 µg/kg in the blanket peats, 101-290 µg/kg in the fresh moorland vegetation, 4186 µg/kg at the burnt site, 17,439 µg/kg in the HSS, 56 ng/L in the stream water and 987 to 7346 µg/kg in the reservoir sediments. No total or individual PAH concentrations exceeded the published sediment quality guidelines. The perylene content of selected moorland vegetation (sphagnum, heather and bilberry) ranged from 10 to 18% as compared to only 2% for the sediment hosted PAH. A comparison of whole and <250 µm fractions from the burnt surface layer revealed a near threefold increase in PAH concentration in the fine fraction and a change in the PAH distribution such that naphthalene>>phenanthrene>2-methylnaphthalene. Elevated total PAH contents were observed close to the blanket peat sediment surface (0-10 cm) and then declined at greater depths. The high PAH content of the HSS was attributed to the high sorption capacity of the organic-rich particles (TOC 25.8% (wt/wt)). The distribution of individual PAH in reservoir cores and HSS was consistent and the results of the principal component analysis and isomeric ratios suggest mainly pyrolytic inputs, from either vegetation burning and coal combustion. A comparison of the reservoir core PAH profiles shows that the source(s) have remained largely unchanged since the reservoir construction in 1929A.D. reflecting consistent moorland management practices.

Developing a methodology for carbon isotope analysis of lacustrine diatoms.

Stable isotope analysis of sedimentary carbon in lakes can help reveal changes in terrestrial and aquatic carbon cycles. A method based on a single, photosynthetic organism, where host effects are minimised, should offer more precision than carbon isotope studies of bulk lake sediments. Here we report the development of a systematic method for use on fossil lacustrine diatom frustules, adapted from previous studies in marine environments. A step-wise cleaning experiment on diatomaceous lake sediments from Lake Challa, near Mount Kilimanjaro, was made to demonstrate the necessary treatment stages to remove external sedimentary carbon. Changes in soluble carbon compounds during these cleaning experiments were measured using gas chromatography/mass spectrometry (GC/MS). The mass spectrometry methods were refined to measure the small percentage of carbon in these samples and details of these methods are presented. Samples of cleaned diatoms containing <1% carbon yielded robust results. Carbon isotope analyses of diatom samples containing different species mixtures were performed and suggested that differences existed, although the effects lay within current experimental error and require further work. Unlike what was found in work on oxygen and silicon isotopes from diatom frustules, mineral contamination had no discernible impact on the diatom carbon isotope ratios from these sediments. The range of values found in the lakes investigated thus far can be interpreted with reference to the supply and nature of carbon from the catchment as well as to the demand generated from lake primary productivity.