Objectives and Design of Central California's 1995 Integrated Monitoring Study of the California Regional PM10/PM2.5 Air Quality Study

ABSTRACT

The 1995 Integrated Monitoring Study (IMS95) is part of the Phase 1 planning efforts for the California Regional PM_10/PM_2.5 Air Quality Study. Thus, the overall objectives of IMS95 are to (1) fill information gaps needed for planning an effective field program later this decade; (2) develop an improved conceptual model for pollution buildup (PM10, PM2.5, and aerosol precursors) in the San Joaquin Valley; (3) develop a uniform air quality, meteorological, and emissions database that can be used to perform initial evaluations of aerosol and fog air quality models; and (4) provide early products that can be used to help with the development of State Implementation Plans for PM_10. Consideration of the new particulate matter standards were also included in the planning and design of IMS95, although they were proposed standards when IMS95 was in the planning process.     

Laboratory and Field Evaluation of Measurement Methods for One-Hour Exposures to O3, PM25, and CO

ABSTRACT

While researchers have linked acute (less than 12-hr) ambient O₃, PM₂₅, and CO concentrations to a variety of adverse health effects, few studies have characterized short-term exposures to these air pollutants, in part due to the lack of sensitive, accurate, and precise sampling technologies. In this paper, we present results from the laboratory and field evaluation of several new (or modified) samplers used in the “roll-around” system (RAS), which was developed to measure 1-hr O₃, PM₂₅, and CO exposures simultaneously. All the field evaluation data were collected during two sampling seasons: the summer of 1998 and the winter of 1999.

To measure 1-hr O₃ exposures, a new active O₃ sampler was developed that uses two nitrite-coated filters to measure O₃ concentrations. Laboratory chamber tests found that the active O₃ sampler performed extremely well, with a collection efficiency of 0.96 that did not vary with temperature or relative humidity (RH). In field collocation comparisons with a reference UV photometric monitor, the active O₃ sampler had an effective collection efficiency ranging between 0.92 and 0.96 and a precision for 1-hr measurements ranging between 4 and 6 parts per billion (ppb). The limits of detection (LOD) of this method were 9 ppb-hr for the chamber tests and ~16 ppb-hr for the field comparison tests.

PM_2.5 and CO concentrations were measured using modified continuous monitors—the DustTrak and the Langan, respectively. A size-selective inlet and a Nafion dryer were placed upstream of the DustTrak inlet to remove particles with aerodynamic diameters greater than 2.5 um and to dry particles prior to the measurements, respectively. During the field validation tests, the DustTrak consistently reported higher PM_2.5 concentrations than those obtained by the collocated 12-hr PM_{2 5} PEM samples, by approximately a factor of 2. After the DustTrak response was corrected (correction factor of 2.07 in the summer and 2.02 in the winter), measurements obtained using these methods agreed well with R² values of 0.87 in the summer and 0.81 in the winter. The results showed that the DustTrak can be used along with integrated measurements to measure the temporal and spatial variation in PM_{2 5} exposures. Finally, during the field validation tests, CO concentrations measured using the Langan were strongly correlated with those obtained using the reference method when the CO levels were above the LOD of the instrument [~1 part per million (ppm)].     

The Kinetics of Catalytic Incineration of Dimethyl Sulfide and Dimethyl Disulfide over an MnO/Fe2O3 Catalyst

ABSTRACT

The catalytic incineration of dimethyl sulfide and dimethyl disulfide [(CH₃)₂S and (CH₃)₂S₂] over an MnO/Fe₂O₃ catalyst was carried out in a bench-scale catalytic incinerator. Three kinetic models (i.e., the power-rate law, the Mars and Van Krevelen model, and the Langmuir-Hinshelwood model) were used to analyze the results. A differential reactor design was used for best fit of kinetic models in this study. The results show that the Langmuir-Hinshelwood model may be feasible to describe the catalytic incineration of (CH₃)₂S and (CH₃)₂S₂. This suggests that the chemical adsorption of O₂ molecules is important in this incineration.     

Identification of Selected Hormonally Active Agents and Animal Mammary Carcinogens in Commercial and Residential Air and Dust Samples

ABSTRACT

In order to characterize typical indoor exposures to chemicals of interest for research on breast cancer and other hormonally mediated health outcomes, methods were developed to analyze air and dust for target compounds that have been identified as animal mammary carcinogens or hormonally active agents and that are used in commercial or consumer products or building materials. These methods were applied to a small number of residential and commercial environments to begin to characterize the extent of exposure to these classes of compounds. Phenolic compounds, including nonylphenol, octylphenol, bisphenol A, and the methoxychlor metabolite 2,2-bis (p-hydroxyphenyl)-1,1,1-trichloroethane (HPTE), were extracted, derivatized, and analyzed by gas chromatography/mass spectrometry (GC/MS)–selective ion monitoring (SIM). Selected phthalates, pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were extracted and analyzed by GC/MS-SIM. Residential and workplace samples showed detectable levels of twelve pesticides in dust and seven in air samples. Phthalates were abundant in dust (0.3524 μg/g) and air (0.005-2.8 μg/m³). Nonylphenol and its mono- and di-ethoxylates were prevalent in dust (0.82-14 μg/g) along with estrogenic phenols such as bisphenol A and o-phenyl phenol. In this 7-sample pilot study, 33 of 86 target compounds were detected in dust, and 24 of 57 target compounds were detected in air. In a single sample from one home, 27 of the target compounds were detected in dust and 15 in air, providing an indication of chemical mixtures to which humans are typically exposed.     

Estrogenic and androgenic activities in total plasma measured with reporter-gene bioassays: relevant exposure measures for endocrine disruptors in epidemiologic studies?

Measurements of estrogenic and androgenic activities in total plasma with Chemically Activated LUciferase gene eXpression (CALUX?) bioassays could provide biologically relevant measures for exposure to endocrine disruptors in epidemiologic studies. The objective of this study was to explore the effects of a variety of sources of potential endocrine disruptors on estrogenic and androgenic activities in total plasma measured by CALUX?. Plasma samples and interview data on sources of potential endocrine disruptors were collected from 108 men with different exposures profiles. CALUX? measurements (BioDetection Services) involved human U2-OS cell lines controlled by the estrogen receptor alpha and the androgen receptor. Mean differences (beta) in 17β-estradiol equivalents (EEQs) and dihydrotestosterone equivalents (AEQs) between exposure groups were estimated using general linear models. Mean plasma AEQs and EEQs were 9.1×10(-1)ng/ml and 12.0pg/ml, respectively. Elevated AEQs were found in smokers (beta 1.9 (95%CI 0.1-3.6)×10(-1)ng/ml) and heavy drinkers (1.4 (0.2-3.1)×10(-1)ng/ml), and in men occupationally exposed to disinfectants (1.6 (0.3-3.5)×10(-1)ng/ml) or welding/soldering fumes (1.4 (-0.2-2.9)×10(-1)ng/ml). Occupational exposure to pesticides, disinfectants, and exhaust fumes seemed to be associated with increased plasma EEQs: 1.5 (-0.2-3.2)pg/ml, 2.1 (0.2-3.9)pg/ml, and 2.9 (0.6-5.2)pg/ml, respectively. Moderate to high plasma dioxin levels, measured in a subgroup by the dioxin-responsive CALUX?, were accompanied by a 20% increase in AEQs. This is the first study in which CALUX? was used to assess hormone activities in total plasma. Although the results are not yet readily interpretable, they indicate that these measurements can be valuable for epidemiologic studies on endocrine disruptors and give direction for further research.     

Spatial and seasonal variations in atrazine and metolachlor surface water concentrations in Ontario (Canada) using ELISA

Concerns regarding the impacts of pesticides on aquatic species and drinking water sources have increased demands on water quality monitoring programs; however the costs of sample analysis can be prohibitive. In this study we investigated enzyme-linked immunosorbent assay (ELISA) as a cost-effective, high through-put method for measuring pesticide concentrations in surface waters. Seven hundred and thirty-nine samples from 158 locations throughout Ontario were analysed for atrazine and metolachlor from April to October 2007. Concentrations ranged from <0.1 to 3.91 μg L⁻¹ (median = 0.12 μg L⁻¹) for atrazine and from <0.1 to 1.83 μg L⁻¹ (median = 0.09 μg L⁻¹) for metolachlor. Peak concentrations occurred in late spring/early summer, in rural agricultural locations, and decreased over the remainder of the growing season for both herbicides. About 3% of the samples that had ELISA results occurring above the limit of quantification (0.10 μg L⁻¹) were evaluated against gas chromatography-mass spectrometry (GC-MS). Linear regression analysis revealed a R² value of 0.88 and 0.39, for atrazine and metolachlor, respectively. ELISA tended to overestimate concentrations for atrazine and metolachlor, most likely because the ELISA kits also detect their metabolites. Atrazine data suggest that ELISA may be used complementary with GC-MS analysis to enhance the spatial and temporal resolution of a water quality monitoring study. The commercially available metolachlor ELISA kit requires further investigation. ELISA may be used to detect atrazine and metolachlor in surface water samples, but it is not recommended as a quantitative replacement for traditional analytical methods.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Spatial distribution of ciguateric fish in the Republic of Kiribati

Ciguatera is food poisoning caused by human consumption of reef fish contaminated with ciguatoxins (CTXs). The expanding international trade of tropical fish species from ciguatera-endemic regions has resulted in increased global incidence of ciguatera, and more than 50 000 people are estimated to suffer from ciguatera each year worldwide. The Republic of Kiribati is located in the Pacific Ocean; two of its islands, Marakei and Tarawa, have been suggested as high-risk areas for ciguatera. The toxicities of coral reef fish collected from these islands, including herbivorous, omnivorous and carnivorous fish (24% [n = 41], 8% [n = 13] and 68% [n = 117], respectively), were analyzed using the mouse neuroblastoma assay (MNA) after CTX extraction. The MNA results indicated that 156 fish specimens, or 91% of the fish samples, were ciguatoxic (CTX levels >0.01 ng g⁻¹). Groupers and moray eels were generally more toxic by an order of magnitude than other fish species. All of the collected individuals of eight species (n = 3-19) were toxic. Toxicity varied within species and among locations by up to 10 000-fold. Cephalapholis argus and Gymnothorax spp. collected from Tarawa Island were significantly less toxic than those from Marakei Island, although all individuals were toxic based on the 0.01 ng g⁻¹ threshold. CTX concentrations in the livers of individuals of two moray eel species (Gymnothorax spp., n = 6) were nine times greater than those in muscle, and toxicity in liver and muscle showed a strong positive correlation with body weight. The present study provides quantitative information on the ciguatoxicity and distribution of toxicity in fish for use in fisheries management and public health.     

Effects of solids retention time on the performance of bioreactors bioaugmented with a 17β-estradiol-utilizing bacterium, Sphingomonas strain KC8

This study investigated the performance of lab-scale sequencing batch reactors (SBRs) that were inoculated with nitrifying activated sludge and bioaugmented with a Sphingomonas strain KC8 (a 17β-estradiol-degrading bacterium). The bioaugmented SBRs were supplied with synthetic wastewater (average initial total organic carbon (TOC) = 175 mg L⁻¹ and average initial ammonia-N = 25 mg L⁻¹) and daily dose of 17β-estradiol (1 mg L⁻¹) and operated under three solid retention times (SRTs) of 5, 10, and 20 d. After three times periods of the operating SRTs, the overall removal of TOC (>87%) and ammonia (>91%) was similar in all the SBRs. Higher 17β-estradiol removals (>99%) were observed for the SBRs. Neither estrogens nor estrogenic activity was detected in the treated water, except some samples from the SBR operating under 5 d of SRT. The ratios of known estrogen degraders (Sphingomonas strain KC8 and ammonia-oxidizing bacteria) and amoA gene to the total bacterial population decreased as SRT increased, suggesting the presence of unknown estrogen-degraders in SBRs operating at SRT = 10 and 20 d. Real-time-terminal-restriction fragment length polymorphism analysis showed that the evenness of microbial community structures was not affected by the SRT; while, the diversity indices suggest that longer SRTs might lead to more diverse microbial community structure. Overall, the results suggested that bioaugmented bioreactors operating at long SRTs (10 and 20 d) were effective in removing 17β-estradiol to the non-estrogenic treatment endpoint.     

Biotic and abiotic degradation of illicit drugs, their precursor, and by-products in soil

This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories.