Application of statistical modeling to optimize a coastal water quality monitoring program

The long-term water quality monitoring program implemented by the Massachusetts Water Resources Authority in 1992 is extensive and has provide substantial understanding of the seasonality of the waters in both Boston Harbor and Massachusetts Bay and the response to improvements in effluent quality and offshore transfer of the effluent in September 2000. The monitoring program was designed with limited knowledge of spatial and temporal variability and long-term trends within the system. This led to an extensive spatial and temporal sampling program. The data through 2003 showed high correlation within physical parameters measured (e.g., salinity, dissolved oxygen) and in biological measures such as chlorophyll fluorescence. To address the potential sampling redundancies in the measurement program, an assessment of the impact of reduced levels of monitoring on the ability to make water quality decisions was completed. The optimization was conducted by applying statistical models that took into account whether there was evidence of a seasonal pattern in the data. The optimization used model survey average readings to identify temporal fixed effects, model survey-average-corrected individual station readings to identify spatial fixed effects, corrected the individual station readings for temporal and spatial fixed effects and derived a correlation model for the corrected data, and applied the correlation model to characterize the correlation of annual average readings from reduced monitoring programs with true parameter levels. Reductions in the number of sampling stations were found less detrimental to the quality of the data for annual decision-making than reductions in the number of surveys per year, although there is less of a difference in this regard for dissolved oxygen than there is for chlorophyll. The analysis led to recommendations for a substantially lower monitoring effort with minimal loss of information. The recommendation supported an annual budget savings of approximately $183,000. Most of the savings was from fewer surveys as approximately $21,000 came from the reduction in the number of stations monitored from 21 to 7 and associated laboratory analytical costs.     

An evaluation of selenium concentrations in water, sediment, invertebrates, and fish from the Solomon River Basin

The Solomon River Basin is located in north-central Kansas in an area underlain by marine geologic shales. Selenium is an indigenous constituent of these shales and is readily leached into the surrounding groundwater. Portions of the Basin are irrigated primarily through the pumping of selenium-contaminated groundwater from wells onto fields in agricultural production. Water, sediment, macroinvertebrates, and fish were collected from various sites in the Basin in 1998 and analyzed for selenium. Selenium concentrations were analyzed spatially and temporally and compared to reported selenium toxic effect thresholds for specific ecosystem components: water, sediments, food-chain organisms, and wholebody fish. A selenium aquatic hazard assessment for the Basin was determined based on protocol established by Lemly. Throughout the Basin, water, macroinvertebrate, and whole fish samples exceeded levels suspected of causing reproductive impairment in fish. Population structures of several fish species implied that successful reproduction was occurring; however, the influence of immigration of fish from low-selenium habitats could not be discounted. Site-specific fish reproduction studies are needed to determine the true impact of selenium on fishery resources in the Basin. The U.S. Government’s right to retain a non-exclusive, royalty free license in and to any copyright is acknowledged.     

Design and evaluation of an inlet conditioner to dry particles for real-time particle sizers

Real-time particle sizers provide rapid information about atmospheric particles, particularly peak exposures, which may be important in the development of adverse health outcomes. However, these instruments are subject to erroneous readings in high-humidity environments when compared with measurements from filter-based, federal reference method (FRM) samplers. Laboratory tests were conducted to evaluate the ability of three inlet conditioners to dry aerosol prior to entering a real-time particle sizer for measuring coarse aerosols (Model 3321 Aerodynamic Particle Sizer, APS) under simulated highly humid conditions. Two 30 day field studies in Birmingham, AL, USA were conducted to compare the response of two APSs operated with and without an inlet conditioner to that measured with FRM samplers. In field studies, the correlation of PM(10-2.5) derived from the APS and that measured with the FRM was substantially stronger with an inlet conditioner applied (r2 ranged from 0.91 to 0.99) than with no conditioner (r2 = 0.61). Laboratory experiments confirmed the ability of the heater and desiccant conditioner to remove particle-borne moisture. In field tests, water was found associated with particles across the sizing range of the APS (0.5 microm to 20 microm) when relative humidity was high in Birmingham. Certain types of inlet conditioners may substantially improve the correlation between particulate mass concentration derived from real-time particle sizers and filter-based samplers in humid conditions.     

Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

Toxic equivalent concentrations (TEQs) for baseline toxicity and specific modes of action as a tool to improve interpretation of ecotoxicity testing of environmental samples

The toxic equivalency concept is a widely applied method to express the toxicity of complex mixtures of compounds that act via receptor-mediated mechanisms such as induction of the arylhydrocarbon or estrogen receptors. Here we propose to extend this concept to baseline toxicity, using the bioluminescence inhibition test with Vibrio fischeri, and an integrative ecotoxicity endpoint, algal growth rate inhibition. Both bioassays were validated by comparison with literature data and quantitative structure-activity relationships (QSARs) for baseline toxicity were developed for all endpoints. The novel combined algae test, with Pseudokirchneriella subcapitata, allows for the simultaneous evaluation of specific inhibition of photosynthesis and growth rate. The contributions of specific inhibition of photosynthesis and non-specific toxicity could be differentiated by comparing the time and endpoint pattern. Photosynthesis efficiency, measured with the saturation pulse method after 2 h of incubation, served as indicator of specific inhibition of photosynthesis by photosystem II inhibitors. Diuron equivalents were defined as toxicity equivalents for this effect. The endpoint of growth rate over 24 h served to derive baseline toxicity equivalent concentrations (baseline-TEQ). By performing binary mixture experiments with reference compounds and complex environmental samples from a sewage treatment plant and a river, the TEQ concept was validated. The proposed method allows for easier interpretation and communication of effect-based water quality monitoring data and provides a basis for comparative analysis with chemical analytical monitoring.     

Preliminary assessment of polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment, including the Firth of Clyde

This paper presents preliminary data on polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment. Sediment and biota (fish liver, fish muscle and mussels) from a number of locations around Scotland were analysed for PBDEs with samples being from both remote and from potentially contaminated areas such as the former sewage sludge dump site at Garroch Head in the Clyde. PBDEs were measured in both cultivated, rope grown mussels and wild mussels collected from 5 sites around Scotland in 2006. Total PBDE concentrations (sum of tri- to hepta-BDEs) ranged from 相似文献   

Development and Parameterization of a Rain- and Fire-driven Model for Exploring Elephant Effects in African Savannas

We describe the development and parameterization of a grid-based model of African savanna vegetation processes. The model was developed with the objective of exploring elephant effects on the diversity of savanna species and structure, and in this formulation concentrates on the relative cover of grass and woody plants, the vertical structure of the woody plant community, and the distribution of these over space. Grid cells are linked by seed dispersal and fire, and environmental variability is included in the form of stochastic rainfall and fire events. The model was parameterized from an extensive review of the African savanna literature; when available, parameter values varied widely. The most plausible set of parameters produced long-term coexistence between woody plants and grass, with the tree–grass balance being more sensitive to changes in parameters influencing demographic processes and drought incidence and response, while less sensitive to fire regime. There was considerable diversity in the woody structure of savanna systems within the range of uncertainty in tree growth rate parameters. Thus, given the paucity of height growth data regarding woody plant species in southern African savannas, managers of natural areas should be cognizant of different tree species growth and damage response attributes when considering whether to act on perceived elephant threats to vegetation.     

Quantitative arsenic speciation in two species of earthworms from a former mine site

The relationship between the total arsenic concentration and the chemical speciation of arsenic in two species of earthworm (Lumbricus rubellus and Dendrodrilus rubidus) in relation to the host soil, was investigated for 13 sites of varying arsenic content, including a background level garden soil and a former mine site at the Devon Great Consols, UK. Earthworms were collected with the host soil (As soil concentration range 16-12, 466 mg kg(-1) dry weight) and measured for their total arsenic (concentration range 7-595 mg kg(-1) dry weight) using inductively coupled plasma mass spectrometry (ICP-MS). A methanol-water mixture was used to extract arsenic species from the earthworms prior to determination of the individual arsenic species by a combination of anion and cation exchange high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A gradient elution anion exchange method is presented whereby nine arsenic species could be measured in one sample injection. Arsenic species were identified by comparison of retention times and sample spiking with known standards and a fully characterised seaweed extract. Arsenic was generally present in the earthworm as arsenate (As(V)) or arsenite (As(III)) and arsenobetaine (AB). Methylarsonate (MA), dimethylarsinate (DMA) and three arsenosugars (glycerol, phosphate, sulfate) were present as minor constituents. These results are discussed in relation to the mechanisms for coping with exposure to soil bound arsenic.     

Origin and characterisation of microparticles in an ice core from the Central Dronning Maud Land, East Antarctica

The scanning electron microscopy-energy dispersive spectroscopic (SEM-EDS) study of selected samples from an ice core collected from Central Dronning Maud Land (CDML), East Antarctica, revealed several microparticles. They are mainly siliceous and carbonaceous particles and have distinct variations in their shape and composition. The morphology and major element chemistry of the particles suggest their origin from either volcanic eruptions or continental dust. The EDS analysis revealed that the volcanic particles are enriched in silica (average SiO2 62%), compared to the continental dust particle (average SiO2 56%). We found that the tephra relating to Agung (1963) and Karkatau (1883) volcanic eruptions, as recorded, in the ice core harbored microbial cells (both coocoid and rods). The occurrence of organic and inorganic particles which bear relation to volcanic eruption and continental dust implies significant environmental changes in the recent past.     

Online detection of waterborne bioavailable copper by valve daily rhythms in freshwater clam Corbicula fluminea

Freshwater clam Corbicula fluminea, a surrogate species in metal toxicity testing, is a promising bioindicator of impairment in aquatic ecosystems. Little is known, however, about the relationship between clam valve daily rhythmic response and metal bioavailability related to a metal biological early warning system (BEWS) design. The purpose of this study was to link biotic ligand model (BLM)-based bioavailability and valve daily rhythm in C. fluminea to design a biomonitoring system for online in situ detection of waterborne copper (Cu). We integrated the Hill-based dose-time-response function and the fitted daily rhythm function of valve closure into a constructed programmatic mechanism. The functional presentation of the present dynamic system was completely demonstrated by employing a LabVIEW graphic control program in a personal computer. We used site-specific effect concentration causing 10% of total valve closure response (EC10) as the detection threshold to implement the proposed C. fluminea-based Cu BEWS. Here our results show that the proposed C. fluminea-based BEWS could be deliberately synthesized to online in situ transmit rapidly the information on waterborne bioavailable Cu levels under various aquatic environmental conditions through monitoring the valve daily rhythmic changes. We suggested that the developed C. fluminea-based dynamic biomonitoring system could assist in developing technically defensible site-specific water quality criteria to promote more efficient uses in water resources for protection of species health in aquatic environments.