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.     

Air quality and deposition of trace elements in Didouche Mourad, Algeria

Total suspended particulate matter and deposition fluxes of particles were investigated in the town of Didouche Mourad which is located 13 km north of Constantine. Samples of air particulate matter were collected at one site located in the heart of the town and situated 3 km north of a cement plant. Samples were collected from 2 November 2002 to 28 April 2003 every 3 days using a high volume air sampler. Sampling intervals were 24 h in all cases. During the same period, samples of dust fallout were collected at the same site. Samples were collected at 30-day intervals. Lead, chromium, manganese, nickel, copper, cobalt and cadmium deposition fluxes were measured and both the soluble and insoluble fractions were determined. Furthermore, the information gathered by this study was correlated with the corresponding hourly weather data provided by a weather station installed at the study station. The possible sources for dust and trace metals were analyzed by comparing average contributions of wind aspects to the concentrations and depositions of mass and chemical species with the average frequencies of wind direction. The mean concentration was 300 μg/m³. The average dust deposition rate through the period of study was 221 mg/(m².day). Results indicate that anthropogenic sources contribute greatly to trace elements. An exposure assessment to the heavy metals taking into account the inhalation route and soil dust ingestion was carried out and allowed direct comparison of trace metal intakes via these routes.     

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.     

Bioaccumulation surveillance in Milford Haven Waterway

Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007–2008. Bioindicator species encompassed various uptake routes—Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources—perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream—giving rise to several significant (negative) relationships between CI and body burdens. Despite the possible influence of salinity gradient as a complicating factor, multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and the biomarkers metallothionein and TOSC). Integrating bioaccumulation data with biological and biochemical endpoints is seen as a useful way to discriminate environmental quality of moderately contaminated areas such as MHW and to prioritise cause and effect investigations.     

On-line dechlorination–hydrogenation of chlorinated paraffin mixtures using GC and GC/MS

Chlorinated paraffins (CPs) are straight chain hydrocarbons that are produced as complex mixtures and are used as flame retardants and paint additives. These mixtures are extremely difficult to characterize using conventional chromatographic methods, as conventional gas chromatography results in unresolved complex chromatograms that preclude the identification and quantification of individual congeners or any reasonable assessment of the average carbon chain length. Carbon chain length is an important parameter for assessing physical properties and the toxicity of these materials. We have modified and improved a previously published gas chromatography–flame ionization detector method that uses Pd catalyst held in the gas chromatograph injector to simultaneously dechlorinate the CPs and separate the resulting alkanes. In addition, we have adapted this method to gas chromatography–mass spectrometry. Dehalogenation of other compounds was also studied with this system to investigate potential application to other complex halogenated mixtures.     

Receptor model-based source apportionment of particulate pollution in Hyderabad, India

Air quality in Hyderabad, India, often exceeds the national ambient air quality standards, especially for particulate matter (PM), which, in 2010, averaged 82.2?±?24.6, 96.2?±?12.1, and 64.3?±?21.2 μg/m³ of PM₁₀, at commercial, industrial, and residential monitoring stations, respectively, exceeding the national ambient standard of 60 μg/m³. In 2005, following an ordinance passed by the Supreme Court of India, a source apportionment study was conducted to quantify source contributions to PM pollution in Hyderabad, using the chemical mass balance (version 8.2) receptor model for 180 ambient samples collected at three stations for PM₁₀ and PM_2.5 size fractions for three seasons. The receptor modeling results indicated that the PM₁₀ pollution is dominated by the direct vehicular exhaust and road dust (more than 60 %). PM_2.5 with higher propensity to enter the human respiratory tracks, has mixed sources of vehicle exhaust, industrial coal combustion, garbage burning, and secondary PM. In order to improve the air quality in the city, these findings demonstrate the need to control emissions from all known sources and particularly focus on the low-hanging fruits like road dust and waste burning, while the technological and institutional advancements in the transport and industrial sectors are bound to enhance efficiencies. Andhra Pradesh Pollution Control Board utilized these results to prepare an air pollution control action plan for the city.