Occurrence of metals in soil and ground water near chromated copper arsenate-treated utility poles

To thoroughly investigate the metal contamination around chromated copper arsenate (CCA)/polyethylene glycol (PEG)-treated utility poles, a total of 189 soil samples obtained from different depths and distances near six treated poles in the Montreal area (Canada) were analyzed for Cu, Cr, and As content. Various soil physicochemical properties were also determined. Ground water samples collected below the poles were analyzed for metals and bioassays with Daphnia magna were conducted. Generally, sandy soils had lower contaminant levels than clayey and organic soils. Copper concentrations in soil were highest followed by As and Cr. The highest Cu (1460 +/- 677 mg kg(-1)), As (410 +/- 150 mg kg(-1)), and Cr (287 +/- 32 mg kg(-1)) concentrations were found at the ground line and immediately adjacent to the pole. Contaminant levels then decreased with distance, approaching background levels within 0.1 m from the pole for Cr and 0.5 m for Cu and As. Chromium and Cu levels generally approached background levels at a depth of 0.5 m. Average As content near the pole on all study sites was three to eight times higher than Quebec's Level C criterion (50 mg kg(-1)), although it dropped to 31 mg kg(-1) at 0.1 m. Results also showed that As persisted up to 1 m in soil depth (17-54 mg kg(-1)). Copper and Cr concentrations in ground water samples were always <1.000 mg L(-1) and <0.05 mg L(-1), respectively and Cr(VI) was <0.02 mg L(-1). One sample contained an As concentration >0.025 mg L(-1) but bioassays showed that, overall, ground water had a low ecotoxic potential.     

Biomass and nutrient removals from commercial thinning and whole-tree clearcutting of central hardwoods

The objective of this research was to evaluate the impacts of increasing product removal on biomass and nutrient content of a central hardwood forest ecosystem. Commercial thinning, currently the most common harvesting practice in southern New England, was compared with whole-tree clearcutting or maximum aboveground utilization. Using a paired-watershed approach, we studied three adjacent, first-order streams in Connecticut. During the winter of 1981–82, one was whole-tree clearcut, one was commercially thinned, and one was designated as the untreated reference. Before treatment, living and dead biomass and soil on the whole-tree clearcut site contained 578 Mg ha^–1 organic matter, 5 Mg ha^–1 nitrogen, 1 Mg ha^–1 phosphorus, 5 Mg ha^–1 potassium, 4 Mg ha^–1 calcium, and 13 Mg ha^–1 magnesium. An estimated 158 Mg ha^–1 (27% of total organic matter) were removed during the whole-tree harvest. Calcium appeared to be the nutrient most susceptible to depletion with 13% of total site Ca removed in whole-tree clearcut products. In contrast, only 4% (16 Mg ha^–1) of the total organic matter and 2% of the total nutrients were removed from the thinned site. Partial cuts appear to be a reliable management option, in general, for minimizing nutrient depletion and maximizing long-term productivity of central hardwood sites. Additional data are needed to evaluate the long-term impacts of more intensive harvests.     

Assessment of contamination and biomarker responses in two species of herons on the St. Lawrence river

This study was undertaken to validate potential biomarkers of exposure and effects due to chemical contaminants in breedingcolonies of the Great Blue Heron and the Black-crowned Night-Heron on the St. Lawrence River. Eggs and fledglings from both species were collected from many colonies along theRiver. The fledglings from colonies in freshwater and brackishwater were more contaminated by mercury and PCBs than those from estuarine and gulf colonies. With respect to fledglings ofthe two heron species, some morphometric and blood biochemicalmeasurements, including plasma thyroid hormones and retinol, were significantly different among colonies. Significant differences were also observed in liver retinoids, EROD and porphyrins among colonies. The results of this study suggestthat plasma retinoids and thyroid hormones are good biomarkersof exposure and effects, and are sufficiently sensitive to reflect local and regional variations in contamination. Along with the measure of contaminants in egg and plasma, they constitute non-invasive biomarkers which represent an importantcriteria for long term monitoring of wildlife species. It is concluded that the Great Blue Heron is an appropriate sentinelspecies in the surveillance network for the St. Lawrence River.     

Screening of heavy metal containing waste types for use as raw material in Arctic clay-based bricks

In the vulnerable Arctic environment, the impact of especially hazardous wastes can have severe consequences and the reduction and safe handling of these waste types are therefore an important issue. In this study, two groups of heavy metal containing particulate waste materials, municipal solid waste incineration (MSWI) fly and bottom ashes and mine tailings (i.e., residues from the mineral resource industry) from Greenland were screened in order to determine their suitability as secondary resources in clay-based brick production. Small clay discs, containing 20 or 40% of the different particulate waste materials, were fired and material properties and heavy metal leaching tests were conducted before and after firing. Remediation techniques (washing in distilled water and electrodialytical treatment) applied to the fly ash reduced leaching before firing. The mine tailings and bottom ash brick discs obtained satisfactory densities (1669–2007 kg/m³) and open porosities (27.9–39.9%). In contrast, the fly ash brick discs had low densities (1313–1578 kg/m³) and high open porosities (42.1–51. %). However, leaching tests on crushed brick discs revealed that heavy metals generally became more available after firing for all the investigated materials and that further optimisation is therefore necessary prior to incorporation in bricks.     

Leaching of Alkali from Concrete in Contact with Waterways

Concrete is usually the preferred material for construction of structures in contact with water during their service life. Early age exposure to water is beneficial for curing of concrete structures. However, the pollution of water from freshly cast concrete in contact with water has not been investigated in detail. A significant increase in the alkalinity has recently been observed in a stream in contact with freshly installed concrete culverts. High alkalinity has caused distress to fresh water fish in the stream. A preliminary laboratory study was commenced to explore the effect of leaching of alkali into water from freshly placed concrete. Freshly cast concrete specimens were exposed to fresh water, covering a range of conditions observed in the field such as volume of concrete/volume of water, age of exposure and cement content. Analysis of the results indicated that early age contact with fresh concrete can lead to an increase in the pH levels of water up to 11, similar to the levels of pH observed in pore water inside freshly cast concrete. It was noted that until an age of 4 days from casting of concrete, the age of exposure does not significantly affect the changes in the peak pH levels of water. Continuous monitoring of water in contact with concrete also indicated that the pH levels diminish with time, which is attributed to the possible reaction of calcium hydroxide with atmospheric carbon. The paper will present the experimental study, the results, analysis and outcomes as well as planning of a more comprehensive study to observe possible ways of reducing the leaching of alkali from freshly placed concrete.     

Low dose effects and non-monotonic dose responses for endocrine active chemicals: Science to practice workshop: Workshop summary

A workshop was held in Berlin September 12–14th 2012 to assess the state of the science of the data supporting low dose effects and non-monotonic dose responses (“low dose hypothesis”) for chemicals with endocrine activity (endocrine disrupting chemicals or EDCs). This workshop consisted of lectures to present the current state of the science of EDC action and also the risk assessment process. These lectures were followed by breakout sessions to integrate scientists from various backgrounds to discuss in an open and unbiased manner the data supporting the “low dose hypothesis”. While no consensus was reached the robust discussions were helpful to inform both basic scientists and risk assessors on all the issues. There were a number of important ideas developed to help continue the discussion and improve communication over the next few years.     

Development and application of quantitative methods for monitoring dermal and inhalation exposure to propiconazole

Quantitative methods to measure dermal and inhalation exposure to the fungicide propiconazole were developed in the laboratory and applied in the occupational exposure setting for monitoring five farm workers' exposure during pesticide preparation and application to peach crops. Dermal exposure was measured with tape-strips applied to the skin, and the amount of propiconazole was normalized to keratin content in the tape-strip. Inhalation exposure was measured with an OVS tube placed in the worker's breathing-zone during pesticide handling. Samples were analyzed by GC-MS in EI+ mode (limit of detection 6 pg microl(-1)). Dermal exposure ranged from non-detectable to 32.1 +/- 22.6 ng per microg keratin while breathing-zone concentrations varied from 0.2 to 2.2 microg m(-3). A positive correlation was observed between breathing-zone concentrations and ambient air temperature (r2 = 0.87, p < 0.01). Breathing-zone concentrations did not correlate with dermal exposure levels (r2 = 0.11, p = 0.52). Propiconazole levels were below limit of detection when rubber gloves, coveralls, and full-face mask were used. The total-body propiconazole dose, determined for each worker by summing the estimated dermal dose and inhalation dose, ranged from 0.01 to 12 microg per kg body weight per day. Our results show that tape-stripping of the skin and the OVS can be effectively utilized to measure dermal and inhalation exposure to propiconazole, respectively, and that the dermal route of exposure contributed substantially more to the total dose than the inhalation route.     

Organochlorines, brominated flame retardants and mercury levels in six seabird species from the Gulf of St. Lawrence (Canada): Relationships with feeding ecology, migration and molt

Concentrations of organochlorines (OCs), brominated flame retardants (BFRs) and mercury (Hg) were measured in eggs of six seabird species breeding in the Gulf of St. Lawrence, Canada. Stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotopes were used as ecological tracers to measure trophic level and connectivity with benthos, respectively. Concentrations, patterns as well as ecological tracers varied significantly between species. The sum of polychlorinated biphenyls (ΣPCBs) was the most important group measured in all seabird species based on concentration followed generally by the sum of chlorinated pesticides (ΣCPs), the sum of brominated flame retardants (ΣBFRs) and finally total Hg (THg). ΣPCBs, ΣCPs and ΣBFRs increased with trophic level, whereas THg did not. Only ΣBFRs increased with a higher connectivity with the benthos. Seabird species resident to the Great Lakes-St. Lawrence ecosystem showed higher Hg and BFR levels than migratory species. Molt patterns were used to explain variations of contaminant levels.     

Contribution of hydrolysis in the abiotic attenuation of RDX and HMX in coastal waters

Sinking of military ships, dumping of munitions during the two World Wars, and military training have resulted in the undersea deposition of numerous unexploded ordnances (UXOs). Leaching of energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from these UXOs may cause adverse ecological effects so that the long-term fate of these chemicals in the sea should be known. The present study assesses the contribution of alkaline hydrolysis into the natural attenuation of RDX and HMX in coastal waters. Alkaline hydrolysis rates were shown to be unaffected by the presence of sodium chloride, the most common component in marine waters. Kinetic parameters (E(a), ln A, k(2)) quantified for the alkaline hydrolysis of RDX and HMX in deionized water (30-50 degrees C, pH 10-12) agreed relatively well with abiotic degradation rates determined in sterilized natural coastal waters (50 and 60 degrees C, variable salinity) even if the latter were generally slightly faster than the former. Furthermore, similar products (HCHO, NO(2)(-), O(2)NNHCH(2)NHCHO) were obtained on alkaline hydrolysis in deionized water and abiotic degradation in coastal waters. These two findings suggested that degradation of nitramines in sterilized natural coastal waters, away from light, was mainly governed by alkaline hydrolysis. Kinetic calculations using the present parameters showed that alkaline hydrolysis of RDX and HMX in marine waters at 10 degrees C would respectively take 112 +/- 10 and 2408 +/- 217 yr to be completed (99.0%). We concluded that under natural conditions hydrolysis should not contribute significantly to the natural attenuation of HMX in coastal waters whereas it could play an active role in the natural attenuation of RDX.