Determination of arsenic species in fish, crustacean and sediment samples from Thailand using high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS)

Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The stability and recovery of arsenic species under the extraction conditions were also determined by a spiking procedure which included the estuarine sediment reference material. The results show good stability for all species after extraction with a variability of less than 10%. Total concentrations of arsenic in the sediments from the Pak Pa-Nang river catchment and the estuary covered the ranges 7-269 microg g(-1)and 4-20 [micro sign]g g(-1)(dry weight), respectively. AsV was the major species found in all the sediment samples with smaller quantities of AsIII. The presence of the more toxic inorganic forms of arsenic in both sediments and biota samples has implications for human health, particularly as they are readily 'available'.     

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.     

A comparison of X-ray fluorescence and wet chemical analysis of air filter samples from a scrap lead smelting operation

Personal and area air samples were taken at a scrap lead smelter operation in a bullet manufacturing facility. Samples were taken using the 37-mm styrene-acrylonitrile closed-face filter cassette (CFC, the current US standard device for lead sampling), the 37-mm GSP or "cone" sampler, the 25-mm Institute of Occupational Medicine (IOM) inhalable sampler, and the 25-mm Button sampler (developed at the University of Cincinnati). Polyvinylchloride filters were used for sampling. The filters were pre- and post-weighed, and analyzed for lead content using a field-portable X-ray fluorescence (XRF) analyzer. The filters were then extracted with dilute nitric acid in an ultrasonic extraction bath and the solutions were analyzed by inductively coupled plasma optical emission spectroscopy. The 25-mm filters were analyzed using a single XRF reading, while three readings on different parts of the filter were taken from the 37-mm filters. The single reading from the 25-mm filters was adjusted for the nominal area of the filter to obtain the mass loading, while the three readings from the 37-mm filters were inserted into two different algorithms for calculating the mass loadings, and the algorithms were compared. The IOM sampler was designed for material collected in the body of the sampler to be part of the collected sample as well as that on the filter. Therefore, the IOM sampler cassettes were rinsed separately to determine if wall-loss corrections were necessary. All four samplers gave very good correlations between the two analytical methods above the limit of detection of the XRF procedure. The limit of detection for the 25-mm filters (5 microg) was lower than for the 37-mm filters (10 microg). The percentage of XRF results that were within 25% of the corresponding ICP results was evaluated. In addition, the bias from linear regression was estimated. Linear regression for the Button sampler and the IOM sampler using single readings and the GSP using all tested techniques for total filter loading gave acceptable XRF readings at loadings equivalent to sampling at the OSHA 8-hour Action Level and Permissible Exposure Limit. However, the CFC only had acceptable results when the center reading corrected for filter area was used, which was surprising, and may be a result of a limited data set. In addition to linear regression, simple estimation of bias indicated reasonable agreements between XRF and ICP results for single XRF readings on the Button sampler filters, (82% of the individual results within criterion), and on the IOM sampler filters (77% or 61%--see text), and on the GSP sampler filters using the OSHA algorithm (78%). As a result of this pilot project, all three samplers were considered suitable for inclusion in further field research studies.     

Economic development and environmental protection: an ecological economics perspective

This paper argues on both theoretical and empirical grounds that, beyond a certain point, there is an unavoidable conflictbetween economic development (generally taken to mean 'materialeconomic growth') and environmental protection. Think for a moment of natural forests, grasslands, marine estuaries, salt marshes, and coral reefs; and of arable soils, aquifers, mineraldeposits, petroleum, and coal. These are all forms of 'natural capital' that represent highly-ordered self-producing ecosystemsor rich accumulations of energy/matter with high use potential (low entropy). Now contemplate despoiled landscapes, eroding farmlands, depleted fisheries, anthropogenic greenhouse gases,acid rain, poisonous mine tailings and toxic synthetic compounds.These all represent disordered systems or degraded forms of energy and matter with little use potential (high entropy). The main thing connecting these two states is human economic activity. Ecological economics interprets the environment-economyrelationship in terms of the second law of thermodynamics. The second law sees economic activity as a dissipative process. Fromthis perspective, the production of economic goods andservices invariably requires the consumption of available energy and matter. To grow and develop, the economynecessarily 'feeds' on sources of high-quality energy/matter first produced by nature. This tends to disorder and homogenizethe ecosphere, The ascendance of humankind has consistently been accompanied by an accelerating rate of ecological degradation, particularly biodiversity loss, the simplificationof natural systems and pollution. In short, contemporary political rhetoric to the contrary, the prevailing growth-oriented global development paradigm is fundamentally incompatible with long-term ecological and social sustainability. Unsustainability is not a technical nor economic problem as usually conceived, but rather a state of systemic incompatibilitybetween a economy that is a fully-contained, growing, dependent sub-system of a non-growing ecosphere. Potential solutions fly inthe face of contemporary development trends and cultural values.     

Conservation and management applications of the REEF volunteer fish monitoring program

The REEF Fish Survey Project is a volunteer fish monitoring program developed by the Reef Environmental Education Foundation (REEF). REEF volunteers collect fish distribution and abundance data using a standardized visual method during regular diving and snorkeling activities. Survey data are recorded on preprinted data sheets that are returned to REEF and optically digitized. Data are housed in a publicly accessible database on REEF's Web site (http: //www.reef.org). Since the project's inception in 1993, over 40,000 surveys have been conducted in the coastal waters of North America, tropical western Atlantic, Gulf of California and Hawaii. The Fish Survey Project has been incorporated into existing monitoring programs through partnerships with government agencies, scientists, conservation organizations, and private institutions. REEF's partners benefit from the educational value and increased stewardship resulting from volunteer data collection. Applications of the data include an evaluation of fish/habitat interactions in the Florida Keys National Marine Sanctuary, the development of a multi-species trend analysis method to identify sites of management concern, assessment of the current distribution of species, status reports on fish assemblages of marine parks, and the evaluation of no-take zones in the Florida Keys. REEF's collaboration with a variety of partners, combined with the Fish Survey Project's standardized census method and database management system, has resulted in a successful citizen science monitoring program.     

Trace Metal Concentration in Roadside Surface Soil and Tree Back: A Measurement of Local Atmospheric Pollution in Abuja, Nigeria

Cadmium, copper, lead, nickel and zinc concentrations were analysed by atomic absorption spectrophotometry in surface soil and tree bark from different districts of Abuja, Nigeria, in order to determine the atmospheric trace metal input in the area.Elevated concentrations of some of the studied metals were observed in the soil and tree bark samples from the commercial/high traffic areas of the city compared to backgroundvalues. In soil samples, the average concentration of the metals were 0.6±0.4, 18.0±4.0, 281±39, 16±4 and66±23 g g^-1 dry weight for Cd, Cu, Pb, Ni and Zn, respectively, whilst the average concentrations in tree bark were 0.3±0.2, 12±4, 133±32, 13±3 and 61±10 g g^-1 dry weight for Cd, Cu, Pb, Ni and Zn, respectively. The trend in trace metal levels suggested that automobile emissions are a major source of these metals as the highest concentrations of Pb and Zn were recorded in the commercial areas of the city known for their high traffic densities. The levels of metal in the study area were relativelylow compared to levels found in some larger and older cities in various countries worldwide.     

Application of the benthic index of biotic integrity to environmental monitoring in Chesapeake Bay

The Chesapeake Bay benthic index of biotic integrity (B-IBI) was developed to assess benthic community health and environmental quality in Chesapeake Bay. The B-IBI provides Chesapeake Bay monitoring programs with a uniform tool with which to characterize bay-wide benthic community condition and assess the health of the Bay. A probability-based design permits unbiased annual estimates of areal degradation within the Chesapeake Bay and its tributaries with quantifiable precision. However, of greatest interest to managers is the identification of problem areas most in need of restoration. Here we apply the B-IBI to benthic data collected in the Bay since 1994 to assess benthic community degradation by Chesapeake Bay Program segment and water depth. We used a new B-IBI classification system that improves the reliability of the estimates of degradation. Estimates were produced for 67 Chesapeake Bay Program segments. Greatest degradation was found in areas that are known to experience hypoxia or show toxic contamination, such as the mesohaline portion of the Potomac River, the Patapsco River, and the Maryland mainstem. Logistic regression models revealed increased probability of degraded benthos with depth for the lower Potomac River, Patapsco River, Nanticoke River, lower York River, and the Maryland mainstem. Our assessment of degradation by segment and water depth provided greater resolution of relative condition than previously available, and helped define the extent of degradation in Chesapeake Bay.     

Factors influencing Aerosol Characteristics over Urban Environment

Atmospheric aerosols are an important contributing factor to turbidity in urban areas besides having impact on health. Aerosol characteristics show a high degree of variability in space and time as anthropogenic share of total aerosol loading is quite substantial and is essential to monitor the aerosol features over long time scales. In the present study extensive observations of columnar aerosol optical depth (AOD), total columnar ozone (TCO) and precipitable water content (PWC) have been carried over a tropical urban city of Hyderabad, India. Significant variations of AOD have been observed during course of the day with low values of AOD during morning and evening hours and high values during afternoon hours. Spectral variation of AOD exhibits high AOD at smaller wavelengths and vice versa except a slight enhancement in AOD at 500 nm. Anomalies in AOD, particulate matter and black carbon concentrations have been observed during May, 2003. Back trajectory analysis of air mass during these episodes suggested variation in air mass trajectories. Analysis of the results suggests that air trajectories from land region north of study area cause high loading of atmospheric aerosols. The results are discussed in the paper.