Measuring and monitoring persistent organic pollutants in the context of risk assessment

Due to growing concerns regarding persistent organic pollutants (POPs) in the environment, extensive studies and monitoring programs have been carried out in the last two decades to determine their concentrations in water, sediment, and more recently, in biota. An extensive review and analysis of the existing literature shows that whilst the vast majority of these efforts either attempt to compare (a) spatial changes (to identify "hot spots"), or (b) temporal changes to detect deterioration/improvement occurring in the environment, most studies could not provide sufficient statistical power to estimate concentrations of POPs in the environment and detect spatial and temporal changes. Despite various national POPs standards having been established, there has been a surprising paucity of emphasis in establishing accurate threshold concentrations that indicate potential significant threats to ecosystems and public health. Although most monitoring programs attempt to check compliance through reference to certain "environmental quality objectives", it should be pointed out that many of these established standards are typically associated with a large degree of uncertainty and rely on a large number of assumptions, some of which may be arbitrary. Non-compliance should trigger concern, so that the problem can be tracked down and rectified, but non-compliance must not be interpreted in a simplistic and mechanical way. Contaminants occurring in the physical environment may not necessarily be biologically available, and even when they are bioavailable, they may not necessarily elicit adverse biological effects at the individual or population levels. As such, we here argue that routine monitoring and reporting of abiotic and biotic POPs concentrations could be of limited use, unless such data can be related directly to the assessment of public health and ecological risks. Risk can be inferred from the ratio of predicted environmental concentration (PEC) and the predicted no effect concentration (PNEC). Currently, the paucity of data does not allow accurate estimation of PNEC, and future endeavors should therefore, be devoted to determine the threshold concentrations of POPs that can cause undesirable biological effects on sensitive receivers and important biological components in the receiving environment (e.g. keystone species, populations with high energy flow values, etc.), to enable derivation of PNECs based on solid scientific evidence and reduce uncertainty. Using the threshold body burden of POPs required to elicit damages of lysosomal integrity in the green mussel (Perna virvidis) as an example, we illustrate how measurement of POPs in body tissue could be used in predicting environmental risk in a meaningful way.     

Crystallographic preferred orientation in albite samples deformed experimentally by dislocation and solution precipitation creep

The crystallographic preferred orientations of a series of experimentally deformed fine-grained albite aggregates were measured by synchrotron source X-ray diffraction. Most samples were deformed and extensively recrystallized by low-temperature recrystallization-accommodated dislocation creep. In axial compression as well as simple shear these samples developed weak but distinct crystallographic preferred orientations consistent with intracrystalline slip on {001}<100>; the sheared samples have a marked asymmetry of the <100> maxima with respect to the shear zone boundaries. One sample was axially compressed by solution precipitation creep; it developed a somewhat different but equally strong preferred orientation, perhaps reflecting crystallographic anisotropy in rates of dissolution and growth.     

Postglacial sedimentary record and history of West Hawk Lake crater,Manitoba

West Hawk Lake (WHL) is located within the glacial Lake Agassiz basin, 140 km east of Winnipeg, Manitoba. The small lake lies in a deep, steep-sided, meteorite impact crater, which has been partly filled by 60 m of sediment that today forms a flat floor in the central part of the basin below 111 m of water. Four cores, 5–11 m in length, were collected using a Kullenberg piston gravity corer. All sediment is clay, contains no unconformities, and has low organic content in all but the upper meter. Sample analyses include bulk and clay mineralogy, major and minor elements, TOC, stable isotopes of C, N, and O, pollen, charcoal, diatoms, and floral and faunal macrofossils. The sequence is divided into four units based mainly on thickness and style of lamination, diatoms, and pollen. AMS radiocarbon dates do not provide a clear indication of age in the postglacial sequence; possible explanations include contamination by older organic inwash and downward movement of younger organic acids. A chronological framework was established using only selected AMS dates on plant macrofossils, combined with correlations to dated events outside the basin and paleotopographic reconstructions of Lake Agassiz. The 822 1-cm-thick varves in the lower 8 m of the cored WHL sequence were deposited just prior to 10,000 cal years BP (∼8,900 ¹⁴C years BP), during the glacial Lake Agassiz phase of the lake. The disappearance of dolomite near the top of the varved sequence reflects the reduced influence of Lake Agassiz and the carbonate bedrock and glacial sediment in its catchment. The lowermost varves are barren of organisms, indicating cold and turbid glacial lake waters, but the presence of benthic and planktonic algae in the upper 520 varves indicates warming; this lake phase coincides with a change in clay mineralogy, δ¹⁸O and δ¹³C in cellulose, and in some other parameters. This change may have resulted from a major drawdown in Lake Agassiz when its overflow switched from northwest to east after formation of the Upper Campbell beach of that lake 9,300–9,400 ¹⁴C years ago. The end of thick varve deposition at ∼10,000 cal years BP is related to the opening of a lower eastern outlet of Lake Agassiz and an accompanying drop in West Hawk Lake level. WHL became independent from Lake Agassiz at this time, sedimentation rates dropped, and only ∼2.5 m of sediment was deposited in the next 10,000 years. During the first two centuries of post-Lake Agassiz history, there were anomalies in the diatom assemblage, stable O and C isotopes, magnetic susceptibility, and other parameters, reflecting an unstable watershed. Modern oligotrophic conditions were soon established; charcoal abundance increased in response to the reduced distance to the shoreline and to warmer conditions. Regional warming after ∼9,500 cal years BP is indicated by pollen and diatoms as well as C and O isotope values. Relatively dry conditions are suggested by a rise in pine and decrease in spruce and other vegetation types between 9,500 and 5,000 cal years BP (∼8,500–4,400 ¹⁴C years BP), plus a decrease in δ¹³C_cell values. After this, there was a shift to slightly cooler and wetter conditions. A large increase in organic content and change in elemental concentration in the past several thousand years probably reflects a decline in supply of mineral detritus to the basin and possibly an increase in productivity.     

Characterization of coal maceral concentrates by curie-point pyrolysis mass spectrometry

A set of 30 maceral concentrates consisting of 5 exinites (sporinites), 14 vitrinites and 11 inertinites (fusinites and semifusinites) was analyzed by Curie-point pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis techniques. Seventeen samples, representing sink/flotation concentrates of 7 different coals, were obtained through the British National Coal Board, whereas the remaining samples represent cesium-chloride density-gradient centrifugation fractions of two different U.S. coals prepared at the University of Utah.It is found that vitrinites, (semi)fusinites and, to some extent, sporinites show qualitatively similar rank-related changes, such as a decrease in dihydroxybenzene signals and an increase in napthalene signals with increasing rank. In fact, the overall pyrolysis MS patterns of inertinities show a close similarity to those of vitrinites of corresponding carbon content (as obtained from higher rank coals).Notwithstanding these similarities, however, the presence of basic differences in maceral structure is indicated by relatively minor but characteristic peak series in the liptinite (sporinite) as well as inertinite samples. Whereas inertinite spectra show relatively pronounced peak series at the high mass end of the spectrum which can be tentatively identified as representative of polynuclear aromatic compounds, sporinites are characterized by series of branched aliphatic and/or alicyclic polyenic hydrocarbons, possibly representing isoprenoids and related biomarker compounds.     

The morphology of galactic rings exterior to evolving bars: test-particle simulations

The morphology of the outer rings of early-type spiral galaxies is compared to integrations of massless collisionless particles initially in nearly circular orbits. Particles are perturbed by a quadrupolar gravitational potential corresponding to a growing and secularly evolving bar. We find that outer rings with R1R2 morphology and pseudo-rings are exhibited by the simulations even though they lack gaseous dissipation. Simulations with stronger bars form pseudo-rings earlier and more quickly than those with weaker bars. We find that the R1 ring, perpendicular to the bar, is fragile and dissolves after a few bar rotation periods if the bar pattern speed increases by more than ∼8 per cent, bar strength increases (by ≳140 per cent) after bar growth or the bar is too strong  ( Q_T > 0.3)  . If the bar slows down after formation, pseudo-ring morphology persists and the R2 ring perpendicular to the bar is populated due to resonance capture. The R2 ring remains misaligned with the bar and increases in ellipticity as the bar slows down. The R2 ring becomes scalloped and does not resemble any ringed galaxies if the bar slows down more than 3.5 per cent suggesting that bars decrease in strength before they slow down this much. We compare the morphology of our simulations to B -band images of nine ringed galaxies from the Ohio State University Bright Spiral Galaxy Survey, and we find a reasonable match in morphologies to R1R2' pseudo-rings seen within a few bar rotation periods of bar formation. Some of the features previously interpreted in terms of dissipative models may be due to transient structure associated with recent bar growth and evolution.     

Investigating the impact of sample desiccation on Itrax XRF core scanner signal reproducibility

Sediment samples tend to dry out during storage and are, therefore, stored refrigerated at about 4°C after wrapping in plastic foil. During XRF core scanning however, the samples must be taken out of their cover, increasing the risk of drying and formation of desiccation cracks on the surface. Because scan times can often amount to several hours and at highest resolution may take over a day to complete, the core will progressively dry out during scanning. With this study we aim to increase our understanding of how this slow drying of the samples during scanning and storage influences the XRF signal because of changes in water content, sediment surface topography, and the development of small, but slowly expanding cracks in the sediment core. Results show that the desiccation of samples during scanning and storage influence the XRF measurements in several ways. Most importantly, slow desiccation of the cores results in both a general lowering of the sample surface, and a shortening of the core due to shrinkage. Larger distance between sediment surface and detector leads to increased noise levels and poor reproducibility for many elements, while the shrinking of cores may shift individual data points between runs, resulting in poor reproducibility and offsets between datasets obtained at different times. Moreover, the loss of light elements, such as hydrogen and oxygen, can influence the matrix effect, especially for organic-rich sediment. Because the XRF signals of individual elements are affected to different degrees, these changes may induce artificial shifts and biases in many elemental ratios commonly used for paleoenvironmental reconstruction.     

Analysis of tidal marsh vegetation patterns in two Georgia estuaries using aerial photography and GIS

Aerial photographs and GIS analysis were used to map the distribution of tidal marsh vegetation along the salinity gradients of the estuaries of the Altamaha and Satilla Rivers in coastal Georgia. Vegetation maps were constructed from 1993 U.S. Geological Survey Digital Orthophoto Quarter Quads, 1∶77,000-scale color infrared photographs taken in 1974 and 1∶24,000-scale black and white photographs taken in 1953, Changes between years were identified using a GIS overlay analysis. Four vegetation classifications were identified and groundtruthed with field surveys: salt marsh (areas containing primarilySpartina alterniflora), brackish marsh (Spartina cynosuroides andS. alterniflora), Juncus (Juncus roemerianus), and fresh marsh (Zizania aquatica, Zizaniopsis miliacae, and others). There was no evidence for an upstream shift in marsh vegetation along the longitudinal axis of either estuary over the time frame of this analysis, which implies there has not been a long-term increase in salinity. Although the inland extent of each marsh zone was further upstream in the Satilla than the Altamaha, they corresponded to similar average high tide salinities in each estuary: areas classified as salt marsh occurred from the mouth up to where average high tide salinity in the water was approximately 15 psu;Juncus ranged from 21 to 1 psu; brackish marsh ranged from 15 to 1 psu; and fresh marsh was upstream of 1 psu. Approximately 63% of the 6,786 ha of tidal marsh vegetation mapped in the Altamaha and 75% of the 10,220 ha mapped in the Satilla remained the same in all 3 yr.Juncus was the dominant classification in the intermediate regions of both estuaries, and shifts between areas classified asJuncus and either brackish or salt marsh constituted the primary vegetation change between 1953 and 1993 (87% of the changes observed in the Altamaha and 95% of those in the Satilla). This analysis suggests that the broad distribution of tidal marsh vegetation along these two estuaries is driven by salinity, but that at the local scale these are dynamic systems with a larger number of factors affecting the frequently changing borders of vegetation patches.     

Environmental variability during the Last Interglacial: a new high‐resolution pollen record from Tenaghi Philippon,Greece

A new high‐resolution Last Interglacial pollen record from the Tenaghi Philippon peatland, northeast Greece, documents variability in forest composition and cover, which we attribute to changes in temperature and moisture availability. The declining stage of the interglacial was marked by a stepwise decrease in temperate tree populations and culminated in the complete collapse of forest at the onset of the ensuing stadial. The coincidence of the onset of the stepwise declining trend with the increased prominence of North Atlantic ice‐rafting events suggests that ecological thresholds in southern Europe were only crossed once ice rafting events intensified, and implies that changes in North Atlantic ocean circulation were an important contributing factor to the declining temperate forest cover in southern Europe. Our results provide evidence for intra‐interglacial variability in the low mid latitudes and suggest a coupling between the high northern latitudes and the northeast Mediterranean during this interval. Copyright © 2013 John Wiley & Sons, Ltd.     

Cut-off Lows in the South Africa region and their contribution to precipitation

The contribution of Cut-off Lows (CoLs) to precipitation and extreme rainfall frequency in South Africa has been quantified from 402 station records over the period 1979–2006. Firstly, 500 hPa CoL trajectories over Southern Africa and surrounding oceans were determined and their features thoroughly analyzed. In a second step, using daily precipitable water, outgoing long wave radiation data and station rainfall records, an area was defined where the occurrence of CoLs is associated with rainfall over South Africa. CoLs transiting in the 2.5°E–32.5°E/20°S–45°S are more likely to produce precipitation over the country. When 500 hPa CoLs are centered just off the west coast of the country (around 15°E/32.5°S) their impact is substantial in term of daily rainfall intensity and spatial coverage. CoL rainy days have been studied and it is shown that they significantly contribute to precipitation in South Africa, more strongly along the south and east coasts as well as inland, over the transition zone between the summer and winter rainfall domains where they contribute between 25 to more than 35 % of annual accumulation. At the country scale, CoL rainfall is more intense and widespread in spring than during other seasons. Over the analyzed period, a significant trend in annual CoLs’ frequency shows an increase of about 25 %. This increase is mainly realized in spring and in a lesser extent in summer. This trend is accompanied by a significant increase in the frequency of CoL rainy days specifically along the south coast and over the East of the country during the spring–summer period. In parallel, it is shown that from late spring until summer CoLs’ frequency varies significantly accordingly with large scale circulation modes of the Southern Hemisphere such as the Pacific South American pattern (PSA). This positive trend in CoLs’ frequency may be related with the positive trend in the PSA during the spring–summer period over the three last decades.     

Susceptibility of fish to Chattonella marina is determined by its tolerance to hypoxia

The harmful alga Chattonella marina has caused massive fish kills and economic losses worldwide. However, the fish kill mechanisms by C. marina have not been identified. The present study has confirmed that a significant elevation of blood osmolality is the universal response in moribund fish exposed to C. marina and the possible reasons leading to contradictory reports were identified. Both osmotic distress and respiratory impairment are important mechanisms leading to fish kill by C. marina. The susceptibility of marine fish to C. marina appears to be inversely related to their tolerance to hypoxia, with the hypoxia intolerant goldlined seabream being the most susceptible, and the hypoxia tolerant green grouper being the most tolerant to C. marina. Further studies in the marine medaka (Oryzias melastigma) showed that fish susceptibility to C. marina is directly related to susceptibility of the fish to hypoxia, but not related to its tolerance to hypersalinity stress.