Environmental release of dioxins from reservoir sources during beach nourishment programs

In late 1990s, USEPA/FDA made an important connection regarding the presence of elevated levels of dioxins (e.g., 1500 ng kg⁻¹ TEQ) in ball clays mined in Mississippi (USA) from a geological deposit dated to ∼40 million years (Mississippi Embayment) that stretches over several states (northern part of Mississippi to Kentucky) and levels of dioxins in selected animal food sources. Following a recent beach nourishment program along the mid-Atlantic coast of the US, a number of dark gray, blue tinted nuggets of varying sizes were found on beach strands and near the shoreline. Using the presence of these balls of clay (shape, color, and knowledge regarding their use in pottery) on the beach, together with our direct experience analyzing ball clays for dioxins, we made a possible association between these clays and elevated dioxins. Concerns regarding the potential of nourishment programs to cause severe damage to our beaches drove us to test the dioxin content of nourishment exposed clays. A number of the nuggets, along with freshly dredged and deposited sand (collected the morning after nourishment) with the same coloration, and others (sun-bleached), collected approximately 2 weeks after the completion of the nourishment efforts, were analyzed for the presence of PCDD/Fs, PCBs, and selected semi-volatile chlorinated organics. The clay PCDD/F WHO2005-TEQs (dry weight; ND = DL; EMPC = EMPC) ranged from 0.41 to 5.78 ng kg⁻¹ with an average of 2.64 ng kg⁻¹, whereas the sand sample’s TEQs ranged from 0.18 to 0.31 ng kg⁻¹ PCDD/F WHO-2005, with an average of 0.22 ng kg⁻¹. The average total tetra- through octachlorinated dibenzo-p-dioxin concentration was 2700 ng kg⁻¹ (with a maximum of 5800 ng kg⁻¹) for the clays and 8.5 ng kg⁻¹ (with a maximum of 16.8 ng kg⁻¹) for the sand samples. The congener 2,3,7,8-TCDD (TEF = 1) was detected in half of the clay samples (0.11-0.77 ng kg⁻¹). All of the clay and sand samples displayed an unambiguous and dominating 1,4,6,9-chlorination pattern across homolog groups. No other chlorinated aromatics were detected above background levels. The observations, along with the absence or an extremely low level of polychlorinated dibenzofurans, together with the mineralogical analysis, supports the conclusion that off-shore dredging activities are reaching reservoir sources containing dioxin-tainted, smectic/kaolinite clay minerals. Subsequent beach erosion provides additional environmental releases over time, as buried balls of clay from previous nourishment efforts become exposed.     

Chemcatcher and DGT passive sampling devices for regulatory monitoring of trace metals in surface water

This work aimed to evaluate whether the performance of passive sampling devices in measuring time-weighted average (TWA) concentrations supports their application in regulatory monitoring of trace metals in surface waters, such as for the European Union's Water Framework Directive (WFD). The ability of the Chemcatcher and the diffusive gradient in thin film (DGT) device sampler to provide comparable TWA concentrations of Cd, Cu, Ni, Pb and Zn was tested through consecutive and overlapping deployments (7-28 days) in the River Meuse (The Netherlands). In order to evaluate the consistency of these TWA labile metal concentrations, these were assessed against total and filtered concentrations measured at relatively high frequencies by two teams using standard monitoring procedures, and metal species predicted by equilibrium speciation modeling using Visual MINTEQ. For Cd and Zn, the concentrations obtained with filtered water samples and the passive sampling devices were generally similar. The samplers consistently underestimated filtered concentrations of Cu and Ni, in agreement with their respective predicted speciation. For Pb, a small labile fraction was mainly responsible for low sampler accumulation and hence high measurement uncertainty. While only the high frequency of spot sampling procedures enabled the observation of higher Cd concentrations during the first 14 days, consecutive DGT deployments were able to detect it and provide a reasonable estimate of ambient concentrations. The range of concentrations measured by spot and passive sampling, for exposures up to 28 days, demonstrated that both modes of monitoring were equally reliable. Passive sampling provides information that cannot be obtained by a realistic spot sampling frequency and this may impact on the ability to detect trends and assess monitoring data against environmental quality standards when concentrations fluctuate.     

Effects of Mowing and Prescribed Fire on Plant Community Structure and Function in Rare Coastal Sandplains,Nantucket Island,MA, USA

Coastal sandplains provide habitat for a suite of rare and endangered plant and wildlife species in the northeastern United States. These early successional plant communities were maintained by natural and anthropogenic disturbances including salt spray, fire, and livestock grazing, but over the last 150 years, a decrease in anthropogenic disturbance frequency and intensity has resulted in a shift towards woody shrub dominance at the expense of herbaceous taxa. This study quantified the effects of more than a decade of dormant season disturbance-based vegetation management (mowing and prescribed fire) on coastal sandplain plant community composition on Nantucket Island, Massachusetts, USA. We used time-series plant cover data from two similar sites to evaluate the effectiveness of disturbance management for restoring herbaceous species cover and reducing woody shrub dominance. Our results indicate that applying management outside of the peak of the growing season has not been effective in maintaining or increasing the cover of herbaceous species. While management activities resulted in significant (P < 0.01) increases in herbaceous species immediately after treatment, woody species recolonized and dominated treated sites within 3-years post treatment at the expense of graminoids and forbs. These results highlight the difficulties associated with directing ecological succession using disturbance-based management to maintain rare, herbaceous species in coastal sandplain systems that were once a prevalent landscape component under historically chronic anthropogenic disturbance. Further experimentation with growing season disturbance-based management and different combinations of management techniques could provide insights into management alternatives for maintaining herbaceous conservation targets in coastal sandplains.     

Phytoremediation and long-term site management of soil contaminated with pentachlorophenol (PCP) and heavy metals

Pentachlorophenol (PCP) is a persistent organic pollutant (POP) previously used as a timber treatment chemical to prevent sap stain and wood rot. Commonly used in wood treatment industries for the last 50 years, there are now many sites worldwide that are contaminated with PCP. Although persistent, PCP is a mobile contaminant and therefore has a propensity to leach and contaminate surrounding environments. Both willow (Salix sp., 'Tangoio') and poplar (Populus sp. 'Kawa') growing in an open-ended plastic greenhouse were found to tolerate soil PCP concentrations of 250 mg kg(-1) or less and both species stimulated a significant increase in soil microbial activity when compared to unplanted controls. Both poplar and willow could not survive PCP concentrations above 250 mg kg(-1) in soil. Pentachlorophenol degradation occurred in both planted and unplanted pots, but a higher rate of degradation was observed in the planted pots. Soil contaminated by wood-treatment activities often contains co-contaminants such as B, Cr, Cu and As, that are also used as timber preservatives. An additional column leaching experiment, done along side the potted trial, found that PCP, B, Cr, Cu and As were all present in the column leachate. This indicates that although Cu, Cr and As are generally considered immobile in the soil, they were mobilised under our column conditions. If a contaminated site were to be hydraulically 'sealed' using plants, a reticulation irrigation system should be installed to capture any contaminant leachate resulting from heavy rains. This captured leachate can either be independently treated, or reapplied to the site. Our data demonstrate a reduction in soil hydraulic conductivity with repeated application of leachate containing PCP and metal compounds but the soil did not become anaerobic. This would need to be considered in site remediation design.     

Biomonitoring with Gammarus pulex at the Meuse (NL), Aller (GER) and Rhine (F) rivers with the online Multispecies Freshwater Biomonitor

Biological early warning systems represent a set of tools that may be able to respond to certain chemical monitoring requirements of recent European legislation, the Water Framework Directive (WFD2000/60/EC), that aims to improve and protect water quality across Europe. In situ biomonitoring was performed along the rivers Meuse (NL), Aller (GER) and Rhine (F) within the frame of the European Union-funded Project SWIFT-WFD. Gammarus pulex was used as a test organism during the evaluation of the Multispecies Freshwater Biomonitor(R) (MFB), an online biomonitor to quantitatively record different behaviour patterns of animals. At the river Meuse G. pulex reacted to pulse exposure of either a mixture of trace metals or of several organic xenobiotics, by showing up to 20% decreased locomotory activity (already at the 1st pulse) and increased mortality (at 2nd or 3rd pulse only). G. pulex deployed within the MFB system were observed to survive well at the monitoring station on the Aller (100%) and monitoring did not result in the measurement of chemical irregularities. In contrast, deployment at the monitoring station on the Rhine river demonstrated that the test organism was able to detect chemical irregularities by up to 20% decreased locomotory activity in the animals. The MFB proved to be an alert system for water quality monitoring at sensitive sites and sites with accidental pollution.     

Predicting community sensitivity to ozone, using Ellenberg Indicator values

This paper develops a regression-based model for predicting changes in biomass of individual species exposed to ozone (RS(p)), based on their Ellenberg Indicator values. The equation (RS(p)=1.805-0.118Light-0.135 square root Salinity) underpredicts observed sensitivity but has the advantage of widespread applicability to almost 3000 European species. The model was applied to grassland communities to develop two further predictive tools. The first tool, percentage change in biomass (ORI%) was tested on data from a field-based ozone exposure experiment and predicted a 27% decrease in biomass over 5 years compared with an observed decrease of 23%. The second tool, an index of community sensitivity to ozone (CORI), was applied to 48 grassland communities and suggests that community sensitivity to ozone is primarily species-driven. A repeat-sampling routine showed that nine species were the minimum requirement to estimate CORI within 5%.     

A summary of the 209 PCB congener nomenclature

Primary publications of congener numbering shorthand systems for PCB congener identification were reviewed, including the original Ballschmiter-Zell (BZ) system; recommended changes by Schulte and Malisch, and Guitart et al.; and listings by the Chemical Abstracts Service. Comparisons of the various congener numbering shorthands and chlorine substitution numberings in the structural name listings are presented. Several changes, to adhere more closely to IUPAC rules, have been incorporated into the BZ structural nomenclature, and these resulted in renumbering congeners. These corrected listings have been erroneously identified as "IUPAC" numbers, a misnomer, because IUPAC has not published a shorthand system. Guitart pointed out additional inconsistencies with IUPAC rules for nine congeners which would result in further order changes, but did not recommend renumbering, to avoid further confusion. We noted an additional error in the structural name for congener 97, named 2,2',3',4,5 using Ballschmiter and Zell nomenclature and 2,2',3,4',5' using strict IUPAC nomenclature. This renaming would cause the renumbering of the IUPAC number system reported by Guitart for isomers 91 through 98. No further changes are recommended, however. Tables summarizing each publication, and the discrepancies between them are provided in hopes of clarifying the current state of the nomenclature.     

Poplar for the phytomanagement of boron contaminated sites

Boron (B) is a widespread environmental contaminant that is mobile relative to other trace elements. We investigated the potential of hybrid poplar (Populus sp.) for B phytomanagement using a lysimeter experiment and a field trial on B-contaminated wood-waste. In both studies, poplars enhanced evapotranspiration from the wood-waste, reduced B leaching, and accumulated B in the aerial portions of the tree. When grown in a substrate containing 30 mg/kg B, poplar leaves had an average B concentration of 845 mg/kg, while the stems contained 21 mg/kg B. Leaf B concentrations increased linearly with leaf age. A decomposition experiment revealed that abscised leaves released 14% of their B during the winter months. Fertiliser application enhanced tree growth without decreasing the leaf B concentrations. Harvesting alternate rows of trees on a contaminated site would reduce leaching from the site while removing B. Harvested plant material may provide bioenergy, stock fodder, or an amendment for B-deficient soils.     

Physicochemical properties and mineral contents of seven different date fruit (Phoenix dactylifera L.) varieties growing from Saudi Arabia

The date (Phoenix dactylifera L.) fruits (Soukari, Soulag, Barhi, Khulas, Rozaiz, Soughi and Monaif) were evaluated with respect to some physical and chemical properties. While crude protein contents of fruits change between 1.51 % (Soulag) to 2.41 % (Soughi), crude fibre contents ranged between 1.91 % (Soukari) to 3.90 % (Barhi). Vitamin C contents of date samples changed between 971.82 mg/kg (Soughi) to 1,453.15 mg/kg (Barhi). Antioxidant activity of date fruits ranged from 80.07 IC₅₀ (Soukari) to 81.21 IC₅₀ (Soulag). The highest phenolic content was found in Khulas with a mean value of 198 mg GAE/100 g. Energy values of date fruits ranged from 3,725 kcal/kg (Soulag) to 3,870 kcal/kg (Soukari). Sucrose contents of date fruits changed between 1.02 % (Soulag) to 55.71 % (Soukari). Mineral contents of several date fruits were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). Date samples contain potassium at a range between 7,468 mg/kg (Khulas) to 9,619 mg/kg (Soulag). Phosphorus contents of fruits were found between 1,848 mg/kg (Soulag) to 3,066 mg/kg (Rozaiz) and followed by magnesium and calcium. The highest Zn (9.33 mg/kg), Cu (4.27 mg/kg) and Mn (3.26 mg/kg) were found in Rozaiz, Soukari and Barhi samples, respectively.