Spatial variability of organic matter properties determines methane fluxes in a tropical forested peatland.

Tropical peatland ecosystems are a significant component of the global carbon cycle and feature a range of distinct vegetation types, but the extent of links between contrasting plant species, peat biogeochemistry and greenhouse gas fluxes remains unclear. Here we assessed how vegetation affects small scale variation of tropical peatland carbon dynamics by quantifying in situ greenhouse gas emissions over 1 month using the closed chamber technique, and peat organic matter properties using Rock-Eval 6 pyrolysis within the rooting zones of canopy palms and broadleaved evergreen trees. Mean methane fluxes ranged from 0.56 to 1.2 mg m-2 h-1 and were significantly greater closer to plant stems. In addition, pH, ranging from 3.95 to 4.16, was significantly greater closer to stems. A three pool model of organic matter thermal stability (labile, intermediate and passive pools) indicated a large labile pool in surface peat (35-42%), with equivalent carbon stocks of 2236-3065 g m-2. Methane fluxes were driven by overall substrate availability rather than any specific carbon pool. No peat properties correlated with carbon dioxide fluxes, suggesting a significant role for root respiration, aerobic decomposition and/or methane oxidation. These results demonstrate how vegetation type and inputs, and peat organic matter properties are important determinants of small scale spatial variation of methane fluxes in tropical peatlands that are affected by climate and land use change.

PAH, PCB, TPH and mercury in surface sediments of the Delaware River Estuary and Delmarva Peninsula, USA.

Surface sediment concentrations of polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB), total petroleum hydrocarbons (TPH) and mercury, were compared from two areas with contrasting land use history, the industrial Delaware Estuary and the rural Delmarva Peninsula (USA). TPH in the Delaware (38-616mg/kg) and saturate/aromatic fractions suggested petroleum/industrial sources compared to biogenic sources in the Delmarva coastal control (<34-159mg/kg). Within the Delaware the ∑PAH18 ranged from 3749 to 22,324µg/kg with isomeric ratios indicative of petroleum combustion source/s, conversely, those in the Delmarva (5-2139µg/kg) also yielded relatively higher perylene that were consistent with natural background levels derived from vegetation/coal combustion source/s. ∑PCB(tri-hepta) concentrations in the Delmarva (0.6-6.5µg/kg) were less than the threshold effect concentration (TEC), whereas the Delaware had received much higher PCB loading (18.1-136.8µg/kg) as evidenced by a significantly higher amounts in some samples (>TEC).

Bioaccumulation surveillance in Milford Haven Waterway.

Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007-2008. Bioindicator species encompassed various uptake routes-Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources-perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream-giving rise to several significant (negative) relationships between CI and body burdens. Despite the possible influence of salinity gradient as a complicating factor, multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and the biomarkers metallothionein and TOSC). Integrating bioaccumulation data with biological and biochemical endpoints is seen as a useful way to discriminate environmental quality of moderately contaminated areas such as MHW and to prioritise cause and effect investigations.

Chemical signatures of the Anthropocene in the Clyde estuary, UK: sediment-hosted Pb, (207/206)Pb, total petroleum hydrocarbon, polyaromatic hydrocarbon and polychlorinated biphenyl pollution records.

The sediment concentrations of total petroleum hydrocarbons (TPHs), polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), Pb and (207/206)Pb isotope ratios were measured in seven cores from the middle Clyde estuary (Scotland, UK) with an aim of tracking the late Anthropocene. Concentrations of TPHs ranged from 34 to 4386 mg kg(-1), total PAHs from 19 to 16,163 µg kg(-1) and total PCBs between less than 4.3 to 1217 µg kg(-1). Inventories, distributions and isomeric ratios of the organic pollutants were used to reconstruct pollutant histories. Pre-Industrial Revolution and modern non-polluted sediments were characterized by low TPH and PAH values as well as high relative abundance of biogenic-sourced phenanthrene and naphthalene. The increasing industrialization of the Clyde gave rise to elevated PAH concentrations and PAH isomeric ratios characteristic of both grass/wood/coal and petroleum and combustion (specifically petroleum combustion). Overall, PAHs had the longest history of any of the organic contaminants. Increasing TPH concentrations and a concomitant decline in PAHs mirrored the lessening of coal use and increasing reliance on petroleum fuels from about the 1950s. Thereafter, declining hydrocarbon pollution was followed by the onset (1950s), peak (1965-1977) and decline (post-1980s) in total PCB concentrations. Lead concentrations ranged from 6 to 631 mg kg(-1), while (207/206)Pb isotope ratios spanned 0.838-0.876, indicative of various proportions of 'background', British ore/coal and Broken Hill type petrol/industrial lead. A chronology was established using published Pb isotope data for aerosol-derived Pb and applied to the cores.

Sedimentary records of sewage pollution using faecal markers in contrasting peri-urban shallow lakes.

Sewage contamination in shallow lake sediments is of concern because the pathogens, organic matter and nutrients contribute to the deterioration of the water-bodies' health and ecology. Sediment cores from three shallow lakes (Coneries, Church and Clifton Ponds) within Attenborough nature reserve located downstream of sewage treatment works were analysed for TOC, C/N, δ(13)C, δ(15)N, bacterial coliforms and faecal sterols. (210)Pb and (137)Cs activities were used to date the sediments. Elemental analysis suggests that the source of organic matter was algal and down profile changes in δ(13)C indicate a possible decrease in productivity with time which could be due to improvements in sewage treatment. δ(15)N for Coneries Pond are slightly higher than those observed in Church or Clifton and are consistent with a sewage-derived nitrate source which has been diluted by non-sewage sources of N. The similarity in δ(15)N values (+12 ‰ to +10 ‰) indicates that the three ponds were not entirely hydrologically isolated. Analysis by gas chromatography/mass spectrometry (GC/MS) reveals that Coneries Pond had sterol concentrations in the range 20 to 30 µg/g (dry wt.), whereas, those from Clifton and Church Ponds were lower. The highest concentrations of the human-sourced sewage marker 5ß-coprostanol were observed in the top 40 cm of Coneries Pond with values up to 2.2 µg/g. In contrast, Church and Clifton Pond sediments contain only trace amounts throughout. Down-profile comparison of 5ß-coprostanol/cholesterol, 5ß-coprostanol/(5ß-coprostanol+5α-cholestanol) and 5ß-epicoprostanol/coprostanol as well as 5α-cholestanol/cholesterol suggests that Coneries Pond has received appreciable amounts of faecal contamination. Examination of 5ß-stigmastanol (marker for herbivorous/ruminant animals) down core concentrations suggests a recent decrease in manure slurry input to Coneries Pond. The greater concentration of ß-sitosterol in sediments from Church and Clifton Ponds as compared to Coneries is attributed in part to their greater diversity and extent of aquatic plants and avian faeces.

Attenuation of TNT in seawater microcosms.

The ability of two differing marine sediments (one clayey, the other sandy) to attenuate the explosive 2,4,6-trinitrotoluene (TNT), dissolved in intertidal seawater from the eastern English coast of the North Sea, was examined using aerobic microcosms. Analysis of the seawater from the microcosms revealed an initial sharp decline in TNT concentration with clayey sediment in both sterilized (to prevent microbial activity) and unsterilized microcosms. This effect did not occur to such a marked extent in similar sterile and non-sterile sandy sediment microcosms and was attributed mainly to sorption of TNT to the fine clay particles of the clayey sediment. As time progressed, the attenuation of TNT in microcosms containing either type of sediment was found to be less in those that had been sterilized compared with those where microbial action proceeded unhindered. Feeding the microcosms, (i.e. supplying extra carbon sources for the microbial communities), appeared to have a small, but perceptible, enhancing effect upon TNT dissipation. The attenuation of TNT was also measured in large microcosms containing 2.5 L of seawater and no sediment. Analysis of the seawater revealed a gradual decline in TNT concentration in non-sterile and fed microcosms compared to their sterile counterpart. Overall, this laboratory study showed that the attenuation of TNT is slow (half-life in seawater ca.1900 days; half-life sand sediment <700 days; half life in clay sediment 130 days) under conditions commonly encountered in coastal waters of the North Sea.

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in sediments from the Mersey Estuary, U.K.

Sediments from the Mersey Estuary were analysed for polycylic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Total PAH concentrations ranged from 626 to 3766 microg/kg and total PCB concentrations ranged from 36 to 1409 microg/kg. These concentrations are intermediate in comparison to other U.K estuaries with similar histories of industrialisation and urbanisation. The distribution of individual PAHs were consistent throughout the Mersey Estuary, this together with molecular indices suggests mainly pyrolitic inputs, augmented by a variety of industrial petrogenic sources. Comparison of tri-to-hepta PCB congeners revealed multiple sources and inputs throughout the estuary. A sediment core collected in close proximity to Garston Docks revealed the take-off, peak pollutant input and recent decline of PCB pollution. However, a second depth profile of sediments at Ellesmere Port showed little change in total or individual PCB concentrations due to extensive sediment reworking and mixing.

Degradation of lignin in wheat straw during growth of the oyster mushroom (Pleurotus ostreatus) using off-line thermochemolysis with tetramethylammonium hydroxide and solid-state (13)C NMR.

The oyster mushroom (Pleurotus ostreatus) is widely cultivated on wheat straw (Triticum aestivum); however, there is a need to better understand the relationship between the chemical composition of the compost and mushroom growth. Wheat straw was degraded over a period of 63 days by P. ostreatus during which time it was sampled at weekly intervals. Off-line thermochemolysis with tetramethylammonium hydroxide and solid-state (13)C NMR were then used in the molecular characterization of the undegraded wheat straw and the degraded samples. The degraded wheat straw samples had a lower proportion of syringyl- to guaiacyl-derived moieties and cinnamyl- to guaiacyl-derived moieties than the undegraded control. There were increases in both guaiacyl and syringyl acid to aldehyde ratios with composting time, which showed that side-chain oxidation has been mediated by P. ostreatus. The (13)C NMR spectra confirmed the increase in carboxyl content but indicated that the overall lignin and methoxyl contents remained relatively constant, although some nonsystematic variations were observed. The spectra also showed a decrease in amorphous noncellulosic polysaccharides in relation to the crystalline cellulose upon degradation.