Air pollutant contamination and acidification of surface waters in the North York Moors, UK: Multi-proxy evidence from the sediments of a moorland pool

Despite the extensive geographical range of palaeolimnological studies designed to assess the extent of surface water acidification in the United Kingdom during the 1980s, little attention was paid to the status of surface waters in the North York Moors (NYM). In this paper, we present sediment core data from a moorland pool in the NYM that provide a record of air pollution contamination and surface water acidification. The 41-cm-long core was divided into three lithostratigraphic units. The lower two comprise peaty soils and peats, respectively, that date to between approximately 8080 and 6740 cal. BP. The uppermost unit comprises peaty lake muds dating from between approximately ad 1790 and the present day (ad 2006). The lower two units contain pollen dominated by forest taxa, whereas the uppermost unit contains pollen indicative of open landscape conditions similar to those of the present. Heavy metal, spheroidal carbonaceous particle, mineral magnetics and stable isotope analysis of the upper sediments show clear evidence of contamination by air pollutants derived from fossil-fuel combustion over the last c. 150years, and diatom analysis indicates that the naturally acidic pool became more acidic during the 20th century. We conclude that the exceptionally acidic surface waters of the pool at present (pH=c. 4.1) are the result of a long history of air pollution and not because of naturally acidic local conditions. We argue that the highly acidic surface waters elsewhere in the NYM are similarly acidified and that the lack of evidence of significant recovery from acidification, despite major reductions in the emissions of acidic gases that have taken place over the last c. 30years, indicates the continuing influence of pollutant sulphur stored in catchment peats, a legacy of over 150years of acid deposition.

One size fits all: stability of metabolic scaling under warming and ocean acidification in echinoderms

Responses by marine species to ocean acidification (OA) have recently been shown to be modulated by external factors including temperature, food supply and salinity. However the role of a fundamental biological parameter relevant to all organisms, that of body size, in governing responses to multiple stressors has been almost entirely overlooked. Recent consensus suggests allometric scaling of metabolism with body size differs between species, the commonly cited 'universal' mass scaling exponent (b) of A3/4 representing an average of exponents that naturally vary. One model, the Metabolic-Level Boundaries hypothesis, provides a testable prediction: that b will decrease within species under increasing temperature. However, no previous studies have examined how metabolic scaling may be directly affected by OA. We acclimated a wide body-mass range of three common NE Atlantic echinoderms (the sea star Asterias rubens, the brittlestars Ophiothrix fragilis and Amphiura filiformis) to two levels of pCO(2) and three temperatures, and metabolic rates were determined using closed-chamber respirometry. The results show that contrary to some models these echinoderm species possess a notable degree of stability in metabolic scaling under different abiotic conditions; the mass scaling exponent (b) varied in value between species, but not within species under different conditions. Additionally, we found no effect of OA on metabolic rates in any species. These data suggest responses to abiotic stressors are not modulated by body size in these species, as reflected in the stability of the metabolic scaling relationship. Such equivalence in response across ontogenetic size ranges has important implications for the stability of ecological food webs.

Seawater acidification by CO2 in a coastal lagoon environment: Effects on life history traits of juvenile mussels Mytilus galloprovincialis

The carbonate chemistry of seawater fromthe Ria Formosa lagoon was experimentallymanipulated, by diffusing pure CO2, to attain two reduced pH levels, by−0.3 and−0.6 pH units, relative to unmanipulated seawater. After 84 days of exposure, no differences were detected in terms of growth (somatic or shell) or mortality of juvenile mussels Mytilus galloprovincialis. The naturally elevated total alkalinity of the seawater (≈3550 μmol kg−1) prevented under-saturation of CaCO3, evenunder pCO2 values exceeding 4000 μatm, attenuating the detrimental effects on the carbonate supply-side. Even so, variations in shell weight showed that net calcification was reduced under elevated CO2 and reduced pH, although the magnitude and significance of this effect varied among size-classes. Most of the loss of shell material probably occurred as post-deposition dissolution in the internal aragonitic nacre layer. Our results show that, even when reared under extreme levels of CO2- induced acidification, juvenileM. galloprovincialis can continue to calcify and grow in this coastal lagoon environment. The complex responses of bivalves to ocean acidification suggest a large degree of interspecific and intraspecific variability in their sensitivity to this type of perturbation. Further research is needed to assess the generality of these patterns and to disentangle the relative contributions of acclimation to local variations in seawater chemistry and genetic adaptation.

Effect of high CO2 and ocean acidification on photosynthesis and response to oxidative stress in seagrasses

Climate change scenarios comprise significant modifications of the marine realm, notably ocean acidification and temperature increase, both direct consequences of the rising atmospheric CO2 concentration. These changes are likely to impact marine organisms and ecosystems, namely the valuable seagrass-dominated coastal habitats. The main objective of this thesis was to evaluate the photosynthetic and antioxidant responses of seagrasses to climate change, considering CO2, temperature and light as key drivers of these processes. The methodologies used to determine global antioxidant capacity and antioxidant enzymatic activity in seagrasses were optimized for the species Cymodocea nodosa and Posidonia oceanica, revealing identical defence mechanisms to those found in terrestrial plants. The detailed analysis and identification of photosynthetic pigments in Halophila ovalis, H.stipulacea, Zostera noltii, Z marina, Z. capricorni, Cymodocea nodosa and Posidonia oceanica, sampled across different climatic zones and depths, also revealed a similarity with terrestrial plants, both in carotenoid composition and in the pigment-based photoprotection mechanisms. Cymodocea nodosa plants from Ria Formosa were submitted to the combined effect of potentially stressful light and temperature ranges and showed considerable physiological tolerance, due to the combination of changes in the antioxidant system, activation of the VAZ cycle and accumulation of leaf soluble sugars, thus preventing the onset of oxidative stress. Cymodocea nodosa plants living in a naturally acidified environment near submarine volcanic vents in Vulcano Island (Italy) showed to be under oxidative stress despite the enhancement of the antioxidant capacity, phenolics concentration and carotenoids. Posidonia oceanica leaves loaded with epiphytes showed a significant increase in oxidative stress, despite the increase of antioxidant responses and the allocation of energetic resources to these protection mechanisms. Globally, the results show that seagrasses are physiologically able to deal with potentially stressful conditions from different origins, being plastic enough to avoid stress in many situations and to actively promote ulterior defence and repair mechanisms when under effective oxidative stress.

Characterizing the effects of ocean acidification in larval and juvenile Manila clam, Ruditapes philippinarum, using a transcriptomic approach

Ocean acidification as a result of anthropogenic carbon dioxide (CO2) emissions and global climate change poses a risk to the ecological landscape of intertidal and shallow subtidal communities. The organisms that inhabit these waters will have to cope with changing environmental conditions through the appropriate modulation of physiological processes. Calcifying organisms are particularly at risk, as increased atmospheric levels of CO2 in the atmosphere increase the partial pressure of CO2 (pCO2) in the oceans. Increased pCO2 reduces the saturation of carbonate minerals required to form calcified structures. Being able to cope with the increased energetic demand of maintaining these structures, in addition to other vital physiological processes, will be the key driver that determines which organisms will persist. Assessment of larval and juvenile Manila clam mortality and physiology in this study suggests that this species is capable of coping with elevated pCO2 conditions. The use of high throughput sequencing and RNA sequence analysis in larval clams revealed several physiological processes that play important roles in the Manila clam’s ability to tolerate elevated pCO2 conditions during this life stage. Exposure of juvenile Manila clams, acclimated to elevated pCO2 conditions, to a thermal stress revealed that this species might also be capable of coping with multiple stressors associated with global climate change. Manila clams could therefore represent a model for studying physiological mechanisms associated with successful acclimation of populations to ocean acidification.

In vitro evaluation of fibrolytic enzymes as additives for maize (Zea mays L.) silage - II. Effects on rate of acidification, fibre degradation during ensiling and rumen fermentation

A study was carried out to determine the influence of fibrolytic enzymes derived from mesophilic or thermophilic fungal sources, added at ensiling, on time-course fermentation characteristics and in vitro rumen degradation of maize silage. The mesophilic enzyme was a commercial product derived from Trichodenna reesei (L), whereas the thermophilic enzyme was a crude extract produced from Thermoascus aurantiacus (Ta) in this laboratory. The fungus was cultured using maize cobs as a carbon source. The resulting fermentation extract was deionised to remove sugars and characterised for its protein concentration, main and side enzymic activities, optimal pH, protein molecular mass and isoelectric point. In an additional study, both enzymes were added to maize forage (333.5 g DM/kg, 70.0, 469.8, 227.1 and 307.5 g/kg DM of CP, NDF, ADF and starch, respectively) at two levels each, normalized according to xylanase activity, and ensiled in 0.5 kg capacity laboratory minisilos. Duplicate silos were opened at 2, 4, 8, 15, and 60 days after ensiling, and analysed for chemical characteristics. Silages from 60 days were bulked and in vitro gas production (GP) and organic matter degradability (OMD) profiles evaluated using the Reading Pressure Technique (RPT), in a completely randomised design. The crude enzyme extract contained mainly xylanase and endoglucanase activities, with very low levels of exoglucanase, which probably limited hydrolysis of filter paper. The extract contained three major protein bands of between 29 and 55 kDa, with mainly acidic isoelectric points. Ensiling maize with enzymes lowered (P < 0.05) the final silage pH, with this effect being observed throughout the ensiling process. All enzyme treatments reduced (P < 0.05) ADF contents. Treatments including Ta produced more gas (P < 0.05) than the controls after 24 h incubation in vitro, whereas end point gas production at 96 h was not affected. Addition of Ta increased (P < 0.01) OMD after 12 h (410 and 416 g/kg versus 373 g/kg), whereas both L and Ta increased (P < 0.05) OMD after 24 h. Addition of enzymes from mesophilic or thermophilic sources to maize forage at ensiling increased the rate of acidification of the silages and improved in vitro degradation kinetics, suggesting an improvement in the nutritive quality. (C) 2003 Elsevier B.V All rights reserved.

The establishment of heathland vegetation on ex-arable land: the response of Calluna vulgaris to soil acidification

The UK Biodiversity Action Plan has identified the creation of lowland heathland as an important objective. Heathland restoration studies have identified soil pH, elevated soil nutrients and large weed seed banks as major problems in the restoration of heathland vegetation on ex-arable land. Heathland vegetation is usually found on nutrient-poor acidic soils. Creating acidic soil conditions on ex-arable sites thus may produce a suitable environment for the establishment of heath vegetation. Soil acidification by the addition of sulphur has been shown to reduce the soil pH and the availability of nutrients in arable soils. A series of experiments was established to investigate the effects of soil acidification using sulphur on the establishment of Calluna vulgaris and the development of weed vegetation. The application of sulphur at 0.24 kg m(-2) to an arable soil was found to increase the survival rate of C. vulgaris cuttings planted in it. The mechanism of increased C. vulgaris survival appeared to be by sulphur application significantly reducing the cover of arable weeds arising from the soil seed bank. Higher rates of sulphur application (0.36 and 0.48 kg m(-2)) resulted in the death of many C. vidgaris plants. However C. vulgaris seedlings were able to establish successfully on these ex-arable soils within 1824 months following the addition of these levels of sulphur. The application of sulphur appears to offer a practical solution to heathland creation on ex-arable land. However, it may be necessary to provide an interval of between 18 and 24 months between the application of sulphur and the addition of C. vulgaris plants or seeds for the successful establishment of heathland vegetation. (C) 2003 Elsevier Ltd. All rights reserved.

Rapid acidification and alkylation: Redox analysis of the MHC class I pathway

The technique of rapid acidification and alkylation can be used to characterise the redox status of oxidoreductases, and to determine numbers of free cysteine residues within substrate proteins. We have previously used this method to analyse interacting components of the MHC class I pathway, namely ERp57 and tapasin. Here, we have applied rapid acidification alkylation as a novel approach to analysing the redox status of MHC class I molecules. This analysis of the redox status of the MHC class I molecules HLA-A2 and HLA-B27, which is strongly associated with a group of inflammatory arthritic disorders referred to as Spondyloarthropathies, revealed structural and conformational information. We propose that this assay provides a useful tool in the study of in vivo MHC class I structure. (c) 2008 Elsevier B.V. All rights reserved.

Buffering of recovery from acidification by organic acids

In the United Kingdom, as in other regions of Europe and North America, recent decreases in surface water sulphate concentrations, due to reduced sulphur emissions, have coincided with marked increases in dissolved organic carbon (DOC) concentrations. Since many of the compounds comprising DOC are acidic, the resulting increases in organic acidity may have the potential to offset the benefits of a decrease in mineral (sulphate) acidity. To test this, we used a triprotic model of organic acid dissociation to estimate the proportional organic acid buffering of reduced mineral acidity as measured in the 22 lakes and streams monitored by the UK Acid Waters Monitoring Network. For an average non-marine sulphate decrease of 30 μeq l− 1 over 15 years from 1988–2003, we estimate that around 28% was counterbalanced by rising strong organic acids, 20% by rising alkalinity (partly attributable to an increase in weak organic acids), 11% by falling inorganic aluminium and 41% by falling non-marine base cations. The situation is complicated by a concurrent decrease in marine ion concentrations, and the impact this may have had on both DOC and acidity, but results clearly demonstrate that organic acid increases have substantially limited the amount of recovery from acidification (in terms of rising alkalinity and falling aluminium) that have resulted from reducing sulphur emissions. The consistency and magnitude of sulphate and organic acid changes are consistent with a causal link between the two, possibly due to the effects of changing acidity, ionic strength and aluminium concentrations on organic matter solubility. If this is the case, then organic acids can be considered effective but partial buffers to acidity change in organic soils, and this mechanism needs to be considered in assessing and modelling recovery from acidification, and in defining realistic reference conditions. However, large spatial variations in the relative magnitude of organic acid and sulphate changes, notably for low-deposition sites in northwestern areas where organic acid increases apparently exceed non-marine sulphate decreases, suggest that additional factors, such as changes in sea-salt deposition and climatic factors, may be required to explain the full magnitude of DOC increases in UK surface waters.

Influence of drought-induced acidification on the mobility of dissolved organic carbon in peat soils

A strong relationship between dissolved organic carbon (DOC) and sulphate (SO42−) dynamics under drought conditions has been revealed from analysis of a 10-year time series (1993–2002). Soil solution from a blanket peat at 10 cm depth and stream water were collected at biweekly and weekly intervals, respectively, by the Environmental Change Network at Moor House-Upper Teesdale National Nature Reserve in the North Pennine uplands of Britain. DOC concentrations in soil solution and stream water were closely coupled, displaying a strong seasonal cycle with lowest concentrations in early spring and highest in late summer/early autumn. Soil solution DOC correlated strongly with seasonal variations in soil temperature at the same depth 4-weeks prior to sampling. Deviation from this relationship was seen, however, in years with significant water table drawdown (>−25 cm), such that DOC concentrations were up to 60% lower than expected. Periods of drought also resulted in the release of SO42−, because of the oxidation of inorganic/organic sulphur stored in the peat, which was accompanied by a decrease in pH and increase in ionic strength. As both pH and ionic strength are known to control the solubility of DOC, inclusion of a function to account for DOC suppression because of drought-induced acidification accounted for more of the variability of DOC in soil solution (R2=0.81) than temperature alone (R2=0.58). This statistical model of peat soil solution DOC at 10 cm depth was extended to reproduce 74% of the variation in stream DOC over this period. Analysis of annual budgets showed that the soil was the main source of SO42− during droughts, while atmospheric deposition was the main source in other years. Mass balance calculations also showed that most of the DOC originated from the peat. The DOC flux was also lower in the drought years of 1994 and 1995, reflecting low DOC concentrations in soil and stream water. The analysis presented in this paper suggests that lower concentrations of DOC in both soil and stream waters during drought years can be explained in terms of drought-induced acidification. As future climate change scenarios suggest an increase in the magnitude and frequency of drought events, these results imply potential for a related increase in DOC suppression by episodic acidification.

Screening human intestinal Bifidobacterium strains for growth, acidification, EPS production and viscosity potential in low-fat milk

Bifidobacterium strains of human origin were screened for their ability to grow in milk and produce exopolysaccharides (EPS). Bifidobacterium strains were grown in low-fat UHT milk and were evaluated for their growth, acidification properties, EPS production and ability to increase the viscosity of fermented milk. The strains that grew well in milk were strains of Bifidobacterium breve and Bifidobacterium longum and B. longum subsp. longum. Among the 22 strains, EPS was produced by Bifidobacterium bifidum ALM 35, B. breve NCIMB 8807 (UCC 2003), B. longum subsp. infantis CCUG 52486 and Bifidobacterium infantis NCIMB 702205 at concentrations ranging from 25 to 140 . The molecular mass and the composition varied considerably, depending on the strain. Analysis of the correlation between the apparent viscosity of the fermented milk and pH indicated that the EPS produced during the acidification of milk possibly contributed to the viscosity of the milk products.

Effect of dairy-based protein sources and temperature on growth, acidification and exopolysaccharide production of Bifidobacterium strains in skim milk

The aim of the present study was to find out the best growing conditions for exopolysaccharide (EPS) producing bifidobacteria, which improve their functionality in yoghurt-like products. Two Bifidobacterium strains were used in this study, Bifidobacterium longum subsp. infantis CCUG 52486 and Bifidobacterium infantis NCIMB 702205. In the first part of the study the effect of casein hydrolysate, lactalbumin hydrolysate, whey protein concentrate and whey protein isolate, added at 1.5% w/v in skim milk, was evaluated in terms of cell growth and EPS production; skim milk supplemented with yeast extract served as the control. Among the various nitrogen sources, casein hydrolysate (CH) showed the highest cell growth and EPS production for both strains after 18 h incubation and therefore it was selected for subsequent work. Based on fermentation experiments using different levels of CH (from 0.5 to 2.5% w/v) it was deduced that 1.5% (w/v) CH resulted in the highest EPS production, yielding 102 and 285 mg L− 1 for B. infantis NCIMB 702205 and B. longum subsp. infantis CCUG 52486, respectively. The influence of temperature on growth and EPS production of both strains was further evaluated at 25, 30, 37 and 42 °C for up to 48 h in milk supplemented with 1.5% (w/v) CH. The temperature had a significant effect on growth, acidification and EPS production. The maximum growth and EPS production were recorded at 37 °C for both strains, whereas no EPS production was observed at 25 °C. Lower EPS production for both strains were observed at 42 °C, which is the common temperature used in yoghurt manufacturing compared to that at 37 °C. The results showed that the culture conditions have a clear effect on the growth, acidification and EPS production, and more specifically, that skim milk supplemented with 1.5% (w/v) CH could be used as a substrate for the growth of EPS-producing bifidobacteria, at 37 °C for 24 h, resulting in the production of a low fat yoghurt-like product with improved functionality.