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.     

Mathematical analysis of the whole core injection method accuracy for measuring phenanthrene biodegradation rates in undisturbed marine sediments

Rates of 14C-phenanthrene mineralization in contaminated, undisturbed marine sediments were measured using the whole core injection method to assess microbial natural attenuation activity as a function of sediment depth. Submerged sediments were sampled from Eagle Harbor, a marine superfund site in Puget Sound. Experiments show significant biodegradation activities (0.0012-0.0036 day(-1)) in the sediment horizons from 0 to 10 cm. The purpose and scope of this paper is to evaluate the range of experimental conditions giving valid results; a mathematical simulation described competing contaminant 14C-phenanthrene diffusion and simultaneous biodegradation (Monod kinetics), both retarded by sorption. The effect of aging was examined with two sorption models in presumed pseudo-homogenous sediments having effective properties. The simulation predictions provide quantitative guidelines for the successful use of the whole core injection method. (1) The effective Monod constant KS' in sediment is increased by a large partition coefficient KP between sediment and water and makes the apparent 14C-phenanthrene biodegradation approach first-order kinetics. (2) When KS'>1 mg(-1) l(-1), the measured 14C-phenanthrene biodegradation extent is biased by inadequately distributed injected tracer only when less than 7% of the sediment horizon is initially probed and mixed with injected tracer. (3) A short incubation time (<20 days) is necessary when a mobile indicator, e.g., gaseous 14CO2, is used. For longer incubation times, predictions show that a 14CO2 indicator diffuses to adjacent horizons, thus smearing the depth profile of biodegradation. (4) This method employing a radiolabeled tracer provides accurate biodegradation rates for freshly contaminated sediments, and represents an upper limit to the natural phenanthrene biodegradation extents if the contaminant is aged over 50 days.