Clear effects of soil organic matter chemistry, as determined by NMR spectroscopy, on the sorption of diuron

Organic matter has long been recognized as the main sorbent phase in soils for hydrophobic organic compounds (HOCs). In recent times, there has been an increasing realization that not only the amount, but also the chemical composition, of organic matter can influence the sorption properties of a soil. Here, we show that the organic carbon-normalized sorption coefficient (K(OC)) for diuron is 27-81% higher in 10 A11 horizons than in 10 matching A12 horizons for soils collected from a small (2ha) field. K(OC) was generally greater for the deeper (B) horizons, although these values may be inflated by sorption of diuron to clays. Organic matter chemistry of the A11 and A12 horizons was determined using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. K(OC) was positively correlated with aryl C (r2=0.59, significance level 0.001) and negatively correlated with O-alkyl C (r2=0.84, significance level <0.001). This is only the second report of correlations between whole soil K(OC) and NMR-derived measures of organic matter chemistry. We suggest that this success may be a consequence of limiting this study to a very small area (a single field). There is growing evidence that interactions between organic matter and clay minerals strongly affect K(OC). However, because the soil mineralogy varies little across the field, the influence of these interactions is greatly diminished, allowing the effect of organic matter chemistry on K(OC) to be seen clearly. This study in some way reconciles studies that show strong correlations between K(OC) and the chemistry of purified organic materials and the general lack of such correlations for whole soils.     

Effect of vegetation type on throughfall deposition and seepage flux

This paper compares different vegetation types (coniferous and deciduous forest, grassed and pure heathland) in terms of input (throughfall deposition) and output (seepage flux) in a region with intermediate nitrogen load (+/-20kg Nha(-1)y(-1) via bulk precipitation) in comparable conditions in north Belgium. Coniferous forest (two plots Pinus sylvestris and two plots Pinus nigra) received significantly higher nitrogen and sulphur throughfall deposition than deciduous forest and heathland. Grassed and pure heathland had significantly highest throughfall quantities of Ca(2+) and Mg(2+), respectively. The observed differences in throughfall deposition between the different vegetation types were not univocally reflected in the ion seepage flux. Considerable seepage fluxes of NO(3)(-), SO(4)(2-), Ca(2+) and Al(III) were only found under the P. nigra plots. We discuss our hypothesis that the P. nigra forests already evolved to a situation of N saturation, while the other vegetation types did not.     

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50tha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50tha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50tha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability.     

Polychlorinated biphenyls (PCBs) and hydroxy-PCBs in adipose tissue of women in Southeast Spain

Polychlorinated biphenyls (PCBs) and hydroxylated PCBs (OH-PCBs) were investigated in human adipose tissue samples collected from 20 women undergoing surgery. Mean sum of PCB and sum of OH-PCB levels were 737ng/g of lipid and 8pg/g of lipid, respectively. Among PCBs, congeners 180, 153, 138 and 170 were the most frequent and abundant, and together constituted 72% of the total amount of PCBs in adipose tissue. The PCB congener pattern and the frequencies and concentrations of non-dioxin-like and non-hydroxylated congeners observed in adipose tissue were similar in distribution and order of magnitude to the profile previously published in Spain but lower than that found in other European countries. Among OH-PCB congeners studied, 4-OH-PCB 107/118 was found at the highest concentrations followed by 3'-OH-PCB 180 and 3-OH-PCB 138. To date, no information on levels of PCB metabolites in the Spanish population is available for comparison. These three predominant OH-PCBs contributed 97% of all OH-PCBs. Twelve dioxin-like PCBs contributed around 8% of the total PCB exposure, and all were present in all study subjects. Further research is required to determine trends in human exposure to PCBs and OH-PCBs and how existing banning measures affect exposure.     

Mobilisation of sediment-associated metals from historical Pb working sites on the River Sheaf, Sheffield, UK

Spatial and temporal patterns of metal mobilisation from former water-powered, Pb working sites in a suburban area of Sheffield (UK) were investigated. Twelve time-integrated mass flux samplers were strategically deployed over two contrasting campaign periods (summer and winter). Suspended sediment samples were characterised magnetically and subjected to metal analysis. Metal levels in the upper River Sheaf showed a marked spatial and temporal variability. Pb concentrations in particular were relatively high (maximum 2132 mg kg(-1)). Their distribution tended to reflect the historical contamination of the valley by 17th to 19th century industry, especially during summer high discharge conditions. The mean suspended sediment Pb concentration (803 mg kg(-1)) exceeds contamination guidelines. It is unclear whether ground remediation of one of the seven floodplain sites in the catchment has been successful. The river is still affected by the legacy of at least two other Pb working sites.     

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.     

Protection of ash (Fraxinus excelsior) trees from ozone injury by ethylenediurea (EDU): roles of biochemical changes and decreased stomatal conductance in enhancement of growth

Treatments with ethylenediurea (EDU) protect plants from ozone foliar injury, but the processes underlying this protection are poorly understood. Adult ash trees (Fraxinus excelsior), with or without foliar ozone symptoms in previous years, were treated with EDU at 450ppm by gravitational trunk infusion in May-September 2005 (32.5ppmh AOT40). At 30-day intervals, shoot growth, gas exchange, chlorophyll a fluorescence, and water potential were determined. In September, several biochemical parameters were measured. The protective influence of EDU was supported by enhancement in the number of leaflets. EDU did not contribute its nitrogen to leaf tissue as a fertiliser, as determined from lack of difference in foliar N between treatments. Both biochemical (increase in ascorbate-peroxidase and ascorbic acid, and decrease in apoplastic hydrogen peroxide) and biophysical (decrease in stomatal conductance) processes regulated EDU action. As total ascorbic acid increased only in the asymptomatic trees, its role in alleviating O(3) effects on leaf growth and visible injury is controversial.     

Interactions of forests with secondary air pollutants: some challenges for future research

The effects of ozone and other photochemical oxidants on individual trees have been studied for several decades, but there has been much less research on the potential effects on entire forest ecosystems. Given that ozone and other oxidants affect the production and subsequent fate of biogenic volatile organic compounds that act as signalling molecules, there is a need for more detailed study of the role of oxidants in modifying trophic interactions in forests. Deposition of fine particulates to forests may act as a source of nutrients, but also changes leaf surface properties, increasing the duration of surface wetness and modifying the habitat for epiphytic organisms, leading to increased risks from pathogens. Even where this pathway contributes a relatively small input of nutrients to forests, the indirect effects on canopy processes and subsequent deposition to the forest floor in throughfall and litter may play a more important role that has yet to be fully investigated.     

Sensitivity analysis of a parameterization of the stomatal component of the DO3SE model for Quercus ilex to estimate ozone fluxes

A sensitivity analysis of a proposed parameterization of the stomatal conductance (g(s)) module of the European ozone deposition model (DO(3)SE) for Quercus ilex was performed. The performance of the model was tested against measured g(s) in the field at three sites in Spain. The best fit of the model was found for those sites, or during those periods, facing no or mild stress conditions, but a worse performance was found under severe drought or temperature stress, mostly occurring at continental sites. The best performance was obtained when both f(phen) and f(SWP) were included. A local parameterization accounting for the lower temperatures recorded in winter and the higher water shortage at the continental sites resulted in a better performance of the model. The overall results indicate that two different parameterizations of the model are needed, one for marine-influenced sites and another one for continental sites.     

In-field variation in 2,4-D mineralization in relation to sorption and soil microbial communities

This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg(-1), the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day(-1) and the total amount of 2,4-D mineralized at 130 days (M(130)) ranged from 24 to 39%. Both k and M(130) were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M(130) were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.