Comparison of phosphorus forms in wet and dried animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy and enzymatic hydrolysis

Both enzymatic hydrolysis and solution (31)P nuclear magnetic resonance (NMR) spectroscopy have been used to characterize P compounds in animal manures. In this study, we comparatively investigated P forms in 0.25 M NaOH/0.05 M EDTA extracts of dairy and poultry manures by the two methods. For the dairy manure, enzymatic hydrolysis revealed that the majority of extracted P was inorganic P (56%), with 10% phytate-like P, 9% simple monoester P, 6% polynucleotide-like P, and 18% non-hydrolyzable P. Similar results were obtained by NMR spectroscopy, which showed that inorganic P was the major P fraction (64-73%), followed by 6% phytic acid, 14 to 22% other monoesters, and 7% phosphodiesters. In the poultry manure, enzymatic hydrolysis showed that inorganic P was the largest fraction (71%), followed by 15% phytate-like P and 1% other monoesters, and 3% polynucleotide-like P. NMR spectroscopy revealed that orthophosphate was 51 to 63% of extracted P, phytic acid 24 to 33%, other phosphomonoesters 6 to 12%, and phospholipids and DNA 2% each. Drying process increased orthophosphate (8.4% of total P) in dairy manure, but decreased orthophosphate (13.3% of total P) in poultry manure, suggesting that drying treatment caused the hydrolysis of some organic P to orthophosphate in dairy manure, but less recovery of orthophosphate in poultry manure. Comparison of these data indicates that the distribution patterns of major P forms in animal manure determined by the two methods were similar. Researchers can utilize the method that best fits their specific research goals or use both methods to obtain a full spectrum of manure P characterization.     

Characterizing the Occurrence,Sources, and Variability of Radon in Pacific Northwest Homes

A compilation of data from earlier studies of 172 homes in the Pacific Northwest indicated that approximately 65 percent of the 46 homes tested in the Spokane River Valley/Rathdrum Prairie region of eastern Washington/northern Idaho had heating season indoor radon (²²²Rn) concentrations above the U. S. EPA guideline of 148 Bq m^?3 (4 pCi L^?1). A subset of 35 homes was selected for additional study. The primary source of indoor radon in the Spokane River Valley/Rathdrum Prairie was pressure-driven flow of soil gas containing moderate radon concentrations (geometric mean concentration of 16,000 Bq m^?3) from the highly permeable soils (geometric mean permeability of 5 × 10^?11 m²) surrounding the house substructures. Estimated soil gas entry rates ranged from 0.4 to 39 m³h^?1 and 1 percent to 21 percent of total building air infiltration. Radon from other sources, including domestic water supplies and building materials was negligible. In high radon homes, winter indoor levels averaged 13 times higher than summer concentrations, while in low radon homes winter levels averaged only 2.5 times higher. Short-term variations in indoor radon were observed to be dependent upon indoor-outdoor temperature differences, wind speed, and operation of forced-air furnace fans. Forced-air furnace operation, along with leaky return ducts and plenums, and openings between the substructure and upper floors enhanced mixing of radon-laden substructure air throughout the rest of the building.     

The New Bedford Harbor Superfund site long-term monitoring program (1993–2009)

New Bedford Harbor (NBH), located in southeastern Massachusetts, was designated as a marine Superfund site in 1983 due to sediment contamination by polychlorinated biphenyls (PCBs). Based on risks to human health and the environment, the first two phases of the site cleanup involved dredging PCB-contaminated sediments from the harbor. Therefore, a long-term monitoring program (LTM) was developed to measure spatial and temporal chemical and biological changes in sediment, water, and biota to assess the effects and effectiveness of the remedial activities. A systematic, probabilistic sampling design was used to select sediment sampling stations. This unbiased design allowed the three segments of the harbor to be compared spatially and temporally to quantify changes resulting from dredging the contaminated sediments. Sediment was collected at each station, and chemical (e.g., PCBs and metals), physical (e.g., grain size), and biological (e.g., benthic community) measurements were conducted on all samples. This paper describes the overall NBH-LTM approach and the results from the five rounds of sample collections. There is a decreasing spatial gradient in sediment PCB concentrations from the northern boundary (upper harbor) to the southern boundary (outer harbor) of the site. Along this same transect, there is an increase in biological condition (e.g., benthic community diversity). Temporally, the contaminant and biological gradients have been maintained since the 1993 baseline collection; however, since the onset of full-scale remediation, PCB concentrations have decreased throughout the site, and one of the benthic community indices has shown significant improvement in the lower and outer harbor areas.     

Accounting for Uncertainty in Risk Assessment: Case Study of Hector's Dolphin Mortality due to Gillnet Entanglement

Abstract: Uncertainties about biological data and human effects often delay decisions on management of endangered species. Some decision makers argue that uncertainty about the risk posed to a species should lead to precautionary decisions, whereas others argue for delaying protective measures until there is strong evidence that a human activity is having a serious effect on the species. We have developed a method that incorporates uncertainty into the estimate of risk so that delays in action can be reduced or eliminated. We illustrate our method with an actual situation of a deadlock over how to manage Hector's dolphin ( Cephalorhychus hectori ). The management question is whether sufficient risk is posed to the dolphins by mortalities in gillnets to warrant regulating the fisheries. In our quantitative risk assessment, we use a population model that incorporates both demographic ( between-individual) and environmental ( between-year) stochasticity. We incorporate uncertainty in estimates of model parameters by repeatedly running the model for different combinations of survival and reproductive rates. Each value is selected at random from a probability distribution that represents the uncertainty in estimating that parameter. Before drawing conclusions, we perform sensitivity analyses to see whether model assumptions alter conclusions and to recommend priorities for future research. In this example, uncertainty did not alter the conclusion that there is a high risk of population decline if current levels of gillnet mortality continue. Sensitivity analyses revealed this to be a robust conclusion. Thus, our analysis removes uncertainty in the scientific data as an excuse for inaction.     

Arizona Hazardous Air Pollutants Monitoring Program

ABSTRACT

In order to evaluate the existing risk to public health in Arizona related to hazardous air pollution, ambient air monitoring for selected hazardous air pollutants (HAPs) was carried out in 1994-1996 in several representative urban and rural areas of Arizona. A wide range of organic HAPs was monitored, requiring a variety of sampling and analysis methods. Stainless steel SUMMA canisters were used for collection of volatile hydrocarbons and halocarbons, which were analyzed by capillary gas chromatography with flame ionization and electron capture detection (GC-FID/ECD). Carbonyl compounds were collected using 2,4-dinitrophenylhydrazine-impregnated cartridges and analyzed by high performance liquid chromatog-raphy with ultraviolet detection. Semi-volatile and non-volatile polycyclic aromatic compounds were collected using a sampling train consisting of a filter followed by a PUF/XAD-4/PUF sandwich cartridge. Following extraction, samples were analyzed by capillary GC with mass spectrometric detection (GC-MS). Database software was developed for data processing and reporting functions. This paper describes the sampling strategy and the sampling and analysis methods employed in the monitoring program and presents a summary of all the results obtained during the duration of the sampling program.     

The levels and composition of persistent organic pollutants in alluvial agriculture soils affected by flooding

The concentrations and composition of persistent organic pollutants (POPs) were determined in alluvial soils subjected to heavy flooding in a rural region of Poland. Soil samples (n?=?30) were collected from the upper soil layer from a 70-km² area. Chemical determinations included basic physicochemical properties and the contents of polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and polycyclic aromatic hydrocarbons (PAHs, 16 compounds). The median concentrations of Σ7PCB (PCB28?+?PCB52?+?PCB101?+?PCB118?+?PCB138?+?PCB153?+?PCB180), Σ3HCH (α-HCH?+?β-HCH?+?γ-HCH) and Σ3pp′(DDT?+?DDE?+?DDD) were 1.60?±?1.03, 0.22?±?0.13 and 25.18?±?82.70 μg kg^?1, respectively. The median concentrations of the most abundant PAHs, phenanthrene, fluoranthene, pyrene, benzo[b]fluoranthene and benzo[a]pyrene were 50?±?37, 38?±?27, 29?±?30, 45?±?36 and 24?±?22 μg kg^?1, respectively. Compared with elsewhere in the world, the overall level of contamination with POPs was low and similar to the levels in agricultural soils from neighbouring countries, except for benzo[a]pyrene and DDT. There was no evidence that flooding affected the levels of POPs in the studied soils. The patterns observed for PAHs and PCBs indicate that atmospheric deposition is the most important long-term source of these contaminants. DDTs were the dominant organochlorine pesticides (up to 99 %), and the contribution of the parent pp′ isomer was up to 50 % of the ΣDDT, which indicates the advantage of aged contamination. A high pp′DDE/pp′DDD ratio suggests the prevalence of aerobic transformations of parent DDT. Dominance of the γ isomer in the HCHs implies historical use of lindane in the area. The effect of soil properties on the POP concentrations was rather weak, although statistically significant links with the content of the <0.02-mm fraction, C_total or N_total were observed for some individual compounds in the PCB group.     

Examination of the Enzyme Resistance of Polyurethane Powder Coatings

Polyurethanes powder lacquers were obtained in a reaction hydroxy terminated polyester resin RUCOTE 102 and blocked polyisocyanate crosslinkers. The polyisocyanates were synthesized using alicyclic diisocyanates (IPDI and H₁₂MDI) and monohydric aliphatic alcohols as well as dibutyltin dilaurate and triethylamine as a catalysts. The biodegradation experiments were realized in solution consisted of lipase (Novozym 735, Novozym 51,032, Lipolase 100L or Palatase 20,000) and phosphate buffer during 42 days at 37 °C. The biodegradation progress was controlled by using optical microscopy method, thermal analysis TG/DTA, DSC method, surface free energy parameters, total organic carbon measurements and sample weight loss. The three-dimensional surface topography of the powder lacquers by means of confocal microscope was investigated. The values of surface roughness parameters were calculated.     

The toxicity of sulfamethazine to Daphnia magna and its additivity to other veterinary sulfonamides and trimethoprim

Sulfonamides (SAs), the oldest chemotherapeutic agents used for antimicrobial therapy, still play an important role in veterinary mass treatments. Consequently, traces of these compounds, alone or in combinations, have been repeatedly detected in the environment. Sulfamethazine (SMZ) deserves particular attention not only because it is the most used veterinary SA, but also due to its proven effects on fertility in mice and on thyroid hormone homeostasis in rats. In this study, after evaluating the acute toxicity to Daphnia magna of six veterinary SAs and trimethoprim (TMP), the additivity of SMZ to each other compound was tested using the isobologram method. Two reproduction tests on the same biological model were also performed in order to derive LOEC and NOEC of SMZ. The acute EC₅₀ was in the range 131–270 mg L⁻¹ for all the compounds tested with the exception of sulfaguanidine (EC₅₀ = 3.86 mg L⁻¹). In acute binary tests SMZ showed a complex interaction with sulfaquinoxaline (superadditivity, additivity or subadditivity) at the three different combination ratios tested, simple additivity to TMP and less than additive interaction when paired to the other SAs. LOEC and NOEC of SMZ obtained from reproduction tests were 3.125 and 1.563 mg L⁻¹, respectively. In conclusion, SMZ should not harm the crustacean population at environmentally realistic concentrations. Its toxicity is comparable to that of other systemic SAs, and their binary interactions are less than additive. The same can not be entirely said for enteric SAs, and considering that these compounds are administered at high doses and mostly excreted in unmetabolised form, further evaluation of their impact to the aquatic environment seems advisable.