Patchy distributions: Optimising sample size

A method for estimating sample size which does not require an a priori definition of desired precision, or the assumption that the population is normally distributed with constant variance, has recently been proposed. This paper discusses this method and presents five modifications which make the method easier to use and reduce the probability of estimating a larger sample size than is actually required. The method is extended and used to estimate the mean abundance of patchily distributed benthic organisms. The technique can be used to guide the design of any environmental sampling programme, be it physical, chemical or biological, where comparisons between times and/or locations are required. Trade-offs between numbers of replicates and numbers of levels/sites are discussed.     

Derivation of Nutrient Guidelines for Streams in Victoria, Australia

Human induced increases to nutrientconcentrations in streams have led to many agenciesdeveloping strategies and criteria for nutrientreduction. National or statewide guidelines aregenerally inappropriate, due to the natural variabilityin stream ecosystems within political boundaries. Thisstudy used an extant aquatic macroinvertebrate-basedregionalisation for the state of Victoria, Australia, asthe basis for defining regions of relatively homogeneousenvironmental character. This enabled the selection ofecologically-based regional reference sites andsubsequent characterisation of the nutrient status ofthese sites. Using an extensive biological and nutrientdata base for streams across the State, we calculated50th and 75th percentile concentrations forreference sites within each region. Using thesepercentiles in conjunction with impact and recoverystudies, we defined nutrient guidelines for each region. Although the nutrient data largely supported thebiological regionalisation, patterns in the nutrient datadid require some minor modifications for the nutrientregions. Relatively unimpacted regions with referencesites in very good-to excellent-condition were assignedguidelines largely based on the 75th percentiles. The more impacted regions, where best availablereference sites were of poorer quality, were assignedguidelines based largely on the 50th percentiles. Professional judgement and known extents of impactsacross each region provided important contributions tothe decision-making process. The derived guidelineconcentrations are comparable to several cited in theliterature and are proposed for use in monitoring,assessment and restoration targets.     

Emissions of gaseous and particulate pollutants in a port and harbour region in India

Ports can generate large quantity of pollutants in the atmosphere due to various activities like loading and unloading,transportation, and construction operations. Determination of the character and quantity of emissions from individual sources is an essential step in any project to control and minimize the emissions.In this study a detailed emission inventory of total suspendedparticulate matter (TSP), particulate matter less than 10 m(PM₁₀), sulfur dioxide (SO₂) and nitrogen oxides (NO_x) for a port and harbour project near Mumbai is compiled. Results show that the total annual average contributions of TSP and PM₁₀ from all the port activitieswere 872 and 221 t yr^-1, respectively. Annual average emissions of gaseous pollutants SO₂ and NO_xwere 56 and 397 t yr^-1, respectively, calculatedby using emission factors for different port activities. The maximum TSP emission (419 t yr ^-1) was from paved roads, while the least (0.4 t yr^-1) was from bulk handling activity. The maximum PM₁₀ emission (123 t yr^-1) was from unpaved roads and minimum (0.2 t yr^-1) from bulk handling operations. Similarly the ratio of TSP and PM₁₀ emission was highest (5.18) from paved roads and least (2.17) from bulk handling operations. Regression relation was derivedfrom existing emission data of TSP and PM₁₀ from variousport activities. Good correlation was observed between TSP andPM₁₀ having regression coefficient >0.8.     

Persistent chlorinated pesticides in fish and cattle fat and their implications for human serum concentrations from the Sene-Gambian region

The concentrations of organochlorine pesticides (OCPs) in fish, shrimps, cattle fat and human serum samples from the Sene-Gambian region were measured using validated analytical methodologies. The results obtained were compared with those of other existing African studies and with data from other developing countries. In fish samples, p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and HCB were detected with a frequency of 100%, whereas p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) was detected in eight, heptachlorepoxide in six and endosulfansulfate in five of the nine fish samples. Relatively low concentrations of OCPs were found in cattle and shrimp fat samples. p,p'-DDE and alpha-hexachlorocyclohexane (alpha-HCH) were the most frequently identified. The sum of HCHs ranged from undetected to 13.3 ng g-1 fat, the sum of DDTs from 11.1 to 199.2 ng g-1 fat and the sum of endosulfans from not detected to 49.7 ng g-1 fat in fish and shrimps. In serum samples, alpha-HCH, p,p'-DDE, o,p'-DDT and p,p'-DDT were detected in all 16 pooled serum samples, whereas endosulfansulfate, methoxychlor, mirex, heptachlorepoxide and endrin were detected in 15 samples with most of the concentrations below 10 ng mL-1. The concentrations of OCPs in human serum were given on a serum lipid and whole serum volume basis. The implications for the human diet of these OCP concentrations in serum were investigated by means of biomagnification factors related to the log Kow values of the targeted compounds. The current use of HCH mixtures was suggested to explain the unusually high alpha-HCH concentration. The distribution pattern of these OCPs in humans was also discussed and compared with that in other studies.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.     

Fate and movement of atrazine, cyanazine, metolachlor and selected degradation products in water resources of the deep Loess Hills of Southwestern Iowa, USA

The environmental fate and movement of herbicides widely used for weed control in corn are assessed for a deep loess soil in southwestern Iowa. Beginning in the early 1980s, the herbicide-based weed control program emphasized the application of atrazine (ATR) or cyanazine (CYN) and metolachlor (MET) for both broadleaf and grass control. Between 1992 and 1995, concentrations of ATR, desethylatrazine (DEA), desisopropylatrazine (DIA), CYN and MET were measured in rainwater, both shallow and deep vadose zone water, and well water. Results show that the frequency of herbicide detections and the range and distribution of occurrences are dependent upon both landscape position and temporal inputs of recharge water from rainfall. Generally, DIA was observed more frequently and in higher mean concentration in well water than DEA, while DEA was observed more frequently than DIA in vadose zone groundwater. A chromatographic analogy is suggested to explain the occurrence patterns observed for both parent herbicide and degradation products within the unsaturated zone water. Analysis of rainwater samples collected during this time also revealed low concentrations of ATR, CYN and MET, with the timing of the detections indicative of non-local transport. Results show that the deep loess soil conducts both water and agricultural chemicals relatively rapidly and as such represents a production system which is vulnerable to contamination of shallow groundwater by herbicide-derived chemicals. Results also illustrate the importance of including major herbicide degradation products in water resource impact assessment studies.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

A study of the distribution of lead, cadmium and copper between water and kaolin, bentonite and a river sediment

Experiments were carried out to monitor the equilibrium distribution of lead, cadmium and copper between an aqueous phase modelling natural water and a solid phase modelling natural sediment, under varying conditions. The aqueous phase was analysed using ETAAS and differential pulse anodic stripping voltammetry (DPASV), whereas XRD and FTIR were used to study the solid phase. Sorption isotherms at constant pH were measured. Conditional distribution constants were calculated as functions of the pH, the time of equilibration and the amount of solid material. The results obtained stress the need for standardization of the approaches to the study of water-sediment interactions in order to be able to evaluate and compare the extensive data from field measurements and to predict these interactions.