Michael J. Whelan

An investigation of the abnormal metabolic status of synovial fluid from patients with rheumatoid arthritis by high field proton nuclear magnetic resonance spectroscopy.

The 1H Hahn spin‐echo NMR profiles of rheumatoid synovial fluids have been investigated and compared with those of matched serum samples. In addition to markedly elevated lactate and diminished glucose concentrations, inflammatory synovial fluids contained (i) substantially lower levels of NMR‐detectable chylomicron‐ and very‐low‐density‐lipoprotein‐associated triacylglycerols which appear to have a shortened mean chain‐length, and (ii) high concentrations of ketone bodies (predominantly 3‐d‐hydroxybutyrate), relative to those of corresponding paired serum samples. These observations confirm the abnormal metabolic status of the inflamed rheumatoid joint and provide evidence for an increased utilisation of lipids for fuel therein.

Multimedia fate of petroleum hydrocarbons in the soil: Oil matrix of constructed biopiles

A dynamic multimedia fugacity model was used to evaluate the partitioning and fate of petroleum hydrocarbon fractions and aromatic indicator compounds within the soil: oil matrix of three biopiles. Each biopile was characterised by four compartments: air, water, soil solids and non-aqueous phase liquid (NAPL). Equilibrium partitioning in biopile A and B suggested that most fractions resided in the NAPL, with the exception of the aromatic fraction with an equivalent carbon number from 5 to 7 (EC(5-7)). In Biopile C, which had the highest soil organic carbon content (13%), the soil solids were the most important compartment for both light aliphatic fractions (EC(5-6) and EC(6-8)) and aromatic fractions, excluding the EC(16-21) and EC(21-35). Our starting hypothesis was that hydrocarbons do not degrade within the NAPL. This was supported by the agreement between predicted and measured hydrocarbon concentrations in Biopile B when the degradation rate constant in NAPL was set to zero. In all scenarios, biodegradation in soil was predicted as the dominant removal process for all fractions, except for the aliphatic EC(5-6) which was predominantly lost via volatilization. The absence of an explicit NAPL phase in the model yielded a similar prediction of total petroleum hydrocarbon (TPH) behaviour; however the predicted concentrations in the air and water phases were significantly increased with consequent changes in potential mobility. Further comparisons between predictions and measured data, particularly concentrations in the soil mobile phases, are required to ascertain the true value of including an explicit NAPL in models of this kind.

Effects of triclosan on soil microbial respiration.

The antimicrobial substance triclosan has widespread use in personal care products and can enter the terrestrial environment if sewage sludge is applied to soil. The inhibitory effects of triclosan on basal and substrate-induced respiration (SIR) of three different soils were investigated. Soils were dosed and later redosed with four nominal triclosan concentrations, and respiration rates were measured over time. In each soil, a significant depression in basal respiration was noted after initial dosing, followed by a recovery. The initial extent of respiration inhibition was positively related to the triclosan dose, i.e., respiration was most inhibited at highest triclosan concentration. Differences in respiration inhibition between soils at equivalent dose were inversely correlated with organic matter and clay content, suggesting that the bioavailability of triclosan might have been reduced by sorption to organic carbon or by physical protection in micropores. Substrate-induced respiration was also reduced by the addition of triclosan and subsequently recovered. After redosing with triclosan, basal respiration was enhanced in all soils, suggesting that it was acting as a substrate. However, redosing resulted in SIR inhibition in all treatments above 10 mg triclosan kg(-1) in all three soils, although all soils appeared to be more resistant to perturbation than following initial dosing. The present study suggests that triclosan inhibits soil respiration but that a subsequent acclimation of the microbial community occurs.

Farming for Water Quality: Balancing Food Security and Nitrate Pollution in UK River Basins

Widespread pollution of groundwater by nutrients is an externality of modern intensive agriculture. Rising nitrate concentrations in freshwater have been of concern throughout the developed world for several decades. Initial worries focused on human health but more recently nitrates role in eutrophication has also become a cause for concern. Because the impact on water quality often comes decades after land use change, the challenge for science is to produce an integrated model of catchment hydrology and quality applicable to the long time-scales involved and that can cope with the complexity of connectivity among land, aquifer, and river. This article discusses the balance between food production, and therefore food security, and protection of water resources. We use recent results from a catchment-scale model of the River Thames in the United Kingdom to demonstrate that the response time of catchments can be on the order of decades, given the delays induced by groundwater flow through aquifers. Historically, the main drivers for changes in N fluxes were massive land use change associated with wartime plowing of permanent pastures and postwar modernization and intensification of agriculture, leading to the current quasi-steady state of N-dependent but leaky agriculture. It is clear that restoration of water quality to mid-twentieth-century levels would require very severe changes in land use and land management, significantly affecting UK food supply and security. Moreover, the potential timescales for recovery are well beyond those of normal political cycles. Failure to act will mean a continued high level of nitrogen transfer to rivers, estuaries, and oceans, with potentially serious ecological implications, and continued emissions greenhouse gases to the atmosphere. Notwithstanding improved efficiency of agronomic methods, the situation is unlikely to change significantly without radical shifts in legislation or farm economics.

Development and application of a catchment scale pesticide fate and transport model for use in drinking water risk assessment

This paper describes the development and application of IMPT (Integrated Model for Pesticide Transport), a parameter-efficient tool for predicting diffuse-source pesticide concentrations in surface waters used for drinking water supply. The model was applied to a small UK headwater catchment with high frequency (8h) pesticide monitoring data and to five larger catchments (479-1653km(2)) with sampling approximately every 14days. Model performance was good for predictions of both flow (Nash Sutcliffe Efficiency generally >0.59 and PBIAS <10%) and pesticide concentrations, although low sampling frequency in the larger catchments is likely to mask the true episodic nature of exposure. The computational efficiency of the model, along with the fact that most of its parameters can be derived from existing national soil property data mean that it can be used to rapidly predict pesticide exposure in multiple surface water resources to support operational and strategic risk assessments.

Predicted persistence and response times of linear and cyclic volatile methylsiloxanes in global and local environments

We investigated the response times of eight volatile methylsiloxanes (VMSs) in environmental systems at different scales from local to global, with a particular focus on overall loss rates after cessation of emissions. In part, this is driven by proposals to restrict the use of some of these compounds in certain products in Europe. The GloboPOP model estimated low absolute Arctic Contamination Potentials for all VMSs and rapid response times in all media except sediment. VMSs are predicted to be distributed predominantly in air where they react with OH radicals, leading to short response times. After cessation of emissions VMSs concentrations in the environment are expected to decrease rapidly from current levels. Response times in specific water and sediment systems were evaluated using a dynamic QWASI model. Response times were sensitive to both physico-chemical properties and environmental characteristics. Degradation was predicted to play the most important role in determining response times in water and sediment. In the case of the lowest molecular weight VMSs such as L2 and D3, response times were essentially independent of environmental characteristics due to fast hydrolysis in water and sediment. However, response times for the other VMSs are system-specific. They are relatively short in shallow water bodies but increase with depth due to the diminishing role of volatilization on concentration change as volume to surface area ratio increases. In sediment, degradation and resuspension rates also contribute most to the response times. The estimated response times for local environments are useful for planning future monitoring programs.

Microbial community composition and activity controls phosphorus transformation in rhizosphere soils of the Yeyahu Wetland in Beijing, China

Microorganisms in the rhizosphere of wetland plants can have a significant impact on phosphorus (P) interception. We investigated the seasonal pattern of microbial community structure and its relationship with different P forms in the rhizosphere of three plants Scirpus planiculmis, Zizania latifolia, and Phragmites australis from the Yeyahu Wetland, China. Chloroform fumigation-extraction was used to determine the soil microbial biomass P (SMBP) and phospholipid fatty acids (PLFA) were used to characterize microbial community composition. P fractions in rhizosphere soil samples were also observed using sequential chemical fractionation. Results showed that the average total PLFA (TPLFA) contents of rhizosphere soils ranged from 34.9 to 40.7nmol·g-1 and were highest in summer. Bacteria were predominant in the rhizospheres of all three plants, accounting for >63% of TPLFA. Aerobic bacteria, represented by 16:0 PLFA, were most abundant. Both organic P (OP) and inorganic P (IP) accumulated in the rhizosphere during the winter die-back phase. Furthermore, both TPLFA and bacterial PLFA decreased with increases in highly resistant OP (HR-OP), occluded P (Oc-P) and Calcium-bound P (Ca-P). This suggests that bacteria play an important role in P transformation and can make use of various P forms. We also found that SMBP was significantly negatively correlated with labile OP (L-OP), moderately labile OP (ML-OP) and HR-OP, reflecting a high degree of cross correlation between SMBP and the PLFA indices.

Predicting Aspergillus fumigatus exposure from composting facilities using a dispersion model: A conditional calibration and validation.

Bioaerosols are released in elevated quantities from composting facilities and are associated with negative health effects, although dose-response relationships are unclear. Exposure levels are difficult to quantify as established sampling methods are costly, time-consuming and current data provide limited temporal and spatial information. Confidence in dispersion model outputs in this context would be advantageous to provide a more detailed exposure assessment. We present the calibration and validation of a recognised atmospheric dispersion model (ADMS) for bioaerosol exposure assessments. The model was calibrated by a trial and error optimisation of observed Aspergillus fumigatus concentrations at different locations around a composting site. Validation was performed using a second dataset of measured concentrations for a different site. The best fit between modelled and measured data was achieved when emissions were represented as a single area source, with a temperature of 29°C. Predicted bioaerosol concentrations were within an order of magnitude of measured values (1000-10,000CFU/m3) at the validation site, once minor adjustments were made to reflect local differences between the sites (r2>0.7 at 150, 300, 500 and 600m downwind of source). Results suggest that calibrated dispersion modelling can be applied to make reasonable predictions of bioaerosol exposures at multiple sites and may be used to inform site regulation and operational management.