The Variability of Estimates of Variance, and Its Effect on Power Analysis in Monitoring Design

Power analysis can be a valuable aid in the design of monitoringprograms. It requires an estimate of variance, which may come from a pilot study or an existing study in a similar habitat. For marine benthic infauna, natural variation in abundances canbe considerable, raising the question of reliability of varianceestimates. We used two existing monitoring programs to generatemultiple estimates of variance. These estimates were found to differ from nominated best estimates by 50% or more in 43% of cases, in turn leading to under or over-estimation of samplesize in the design of a notional monitoring program. The twostudies, from the same general area, using the same samplingmethods and spanning a similar time scale, gave estimatesvarying by more than an order of magnitude for 25% of taxa.We suggest that pilot studies for ecological monitoring programsof marine infauna should include at least two sampling times.     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Formation and Emission of N2O and CH4 from Compost Heaps of Organic Household Waster

Composting can be a source of N₂O andCH₄ production. In this investigation, differentcompost heaps of organic household waste weremonitored with the focus on potential formation ofCH₄ and N₂O in the heaps and emission ofthese gases from the heaps. The studied compost heapshad different compost ages, turning intervals andcompost sizes. The analysed compost gases containedbetween 1–3421 L of N₂O-N L^-1 and 0–470 mL of CH₄ L^-1. The emission rates ofN₂O and CH₄ from the compost heaps werebetween 1–1464 mg N₂O m^-2 day^-1 and0–119 000 mg CH₄ m^-2 day^-1. These verylarge differences in compost gas composition andemission indicate the importance of compostmanagement. The results also give an understanding ofwhere in the composting process an increasing emissionof N₂O and CH₄ can occur.     

Should foliar cadmium concentrations be expressed on a dry weight or dry ash weight basis?

Foliar analysis is a valuable tool for evaluating the pollution status of forests. However, the use of foliar diagnosis in large-scale surveys is a complicated process owing to the high variability within the crown. The method used to express foliar concentrations has often been found to diminish the variability. The effect of the method used to express element concentrations on the spatial variability of cadmium (Cd) in the leaves of crack willow (Salix fragilis L.) was investigated by sampling the leaves of one willow at 292 locations in the crown, each sampling location having a volume of 0.027 m3 (0.3 m x 0.3 m x 0.3 m). Cadmium showed a distinct spatial trend in the crown of the tree. Concentrations as low as 2.4 mg kg(-1) dry weight (DW) or 23.1 mg kg(-1) dry ash weight (DAW) were obtained in the top of the crown, and 10.6 mg kg(-1) DW or 73.0 mg kg(-1) DAW in the bottom of the crown. The lower relative standard deviation and weaker correlation with the sampling height support the use of DAW in large-scale surveys especially. The lower variability of the DAW Cd concentration makes this variable less sensitive to fluctuations caused by differences in growing conditions and sampling methodology. However, the majority of publications in this field report metal concentrations on a DW basis. Therefore, the restrictions set on the use of results expressed on a DAW basis in large-scale surveys of foliar metal concentrations have to be offset against the advantages offered by a reduction of the variability in metal concentrations.     

Nitrogen isotope ratios in pine bark as an indicator of N emissions from anthropogenic sources

The article describes the use of Scots pine bark to identifynitrogen sources in eastern Germany, as well as background areas in Russia and Bulgaria, by using natural isotope ratios of total nitrogen (N_t) and individual N compoundssuch as ammonium (NH₄ ⁺), nitrate (NO₃ ^-)and amid nitrogen (amide-N). The samples collected were analysed using an elemental analyser in connection with a gas isotope mass spectrometer (EA-IRMS). Natural ¹⁵N abundances in pine bark from impact areas suggest that the ammonium accumulated on the surface of the bark is releasedfrom livestock management. Bark of Scots pines growing near agricultural land had highly depleted ¹⁵N_t values (between –8 and –12), while bark from background areas (unpolluted areas) displayed slightly negative ¹⁵N_t values (mean ¹⁵N_t = –3.8). It is assumed that part of the N adsorbed on the bark surface is mainly derived from ammonia(mean ¹⁵N_t = –40.3) escaping from livestock housing and during the application of manure. This assumption is confirmed by experiments under controlled conditions in which manure samples were spread on soil. In addition, temporal and spatial variations of ¹⁵N_t abundances in pine bark from various locations in eastern Germany as wellas pine stands in Nature Park Dübener Heath are discussed.     

Preliminary air pollution monitoring in San Miguel, Buenos Aires

Passive diffusion samplers were employed in San Miguel(Buenos Aires Metropolitan Area) for a preliminary airpollution monitoring. The highest loads were observedin downtown, compared with an urban background site.Total suspended particulate matter (TSPM) varied from0.257 to 0.033 mg cm^-2 month^-1; dust was examinedfor particle nature and size distribution. A similartrend was observed for nitrogen dioxide (NO₂) andTSPM spatial distribution, suggesting that traffic isthe major pollution source. Sulphur dioxide (SO₂)values were low and rather homogeneous. Levels for theinvestigated pollutants are below EPA's guide linevalues. Geographic (flat area, near to Rio de LaPlata) and climatologic factors (rainfalls andvariable wind directions) contribute to disperse pollutants.     

An Evaluation of Selenium Concentrations in Water, Sediment, Invertebrates, and Fish from the Republican River Basin: 1997–1999

The Republican River Basin of Colorado,Nebraska, and Kansas lies in a valley which contains PierreShale as part of its geological substrata. Selenium is anindigenous constituent in the shale and is readily leached intosurrounding groundwater. The Basin is heavily irrigated throughthe pumping of groundwater, some of which is selenium-contaminated, onto fields in agricultural production. Water,sediment, benthic invertebrates, and/or fish were collected from46 sites in the Basin and were analyzed for selenium to determinethe potential for food-chain bioaccumulation, dietary toxicity,and reproductive effects of selenium in biota. Resultingselenium concentrations were compared to published guidelines orbiological effects thresholds. Water from 38% of the sites (n = 18) contained selenium concentrations exceeding 5 g L^-1, which is reported to be a high hazard for selenium accumulation into the planktonic food chain. An additional 12 sites (26% of the sites) contained selenium in water between 3–5 g L^-1, constituting a moderate hazard. Selenium concentrations in sedimentindicated little to no hazard for selenium accumulation fromsediments into the benthic food chain. Ninety-five percent ofbenthic invertebrates collected exhibited selenium concentrationsexceeding 3 g g^-1, a level reported as potentially lethal to fish and birds that consume them. Seventy-five percent of fish collected in 1997, 90% in 1998, and 64% in 1999 exceeded 4 g g^-1selenium, indicating a high potential for toxicity andreproductive effects. However, examination of weight profilesof various species of collected individual fish suggestedsuccessful recruitment in spite of selenium concentrations thatexceeded published biological effects thresholds for health andreproductive success. This finding suggested that universalapplication of published guidelines for selenium may beinappropriate or at least may need refinement for systems similarto the Republican River Basin. Additional research is needed todetermine the true impact of selenium on fish and wildliferesources in the Basin.     

The Monitoring and Risk Assessment of Zn Deposition Around a Metal Smelter in Latvia

Heavy metal concentrations in Hylocomium splendens collected around a metal smelter in Latvia showed very high concentrations of Zn (>200 g/g), and elevated concentrations of Pb (38.3 g/g) and Cu (18.3 g/g). In an attempt to better evaluate the potential toxicity of the high Zn concentrations, a serial elution method was used to determine the concentrations of zinc in intercellular, extracellular exchangeable cell wall, intracellular, and particle fractions. The intercellular Zn concentrations represent the water soluble component of the total concentrations, and were low with no clear trends. Zn concentrations in the extra- and intracellular and particle fractions decreased exponentially from the pollutant source. Intracellular Zn concentrations in moss close to the emission source are within the range considered to be potentially toxic, from other single element exposure studies. The proportion of Zn in the relatively insoluble particle fraction, which is least associated with environmental risk, was greater closer to the pollution source, reaching > 30% in the oldest Hylocomium splendens segments.     

Climate impact on social systems: the risk assessment approach

A novel approach to the problem of estimating climate impact on social systems is suggested. This approach is based on a risk concept, where the notion of critical events is introduced and the probability of such events is estimated. The estimation considers both the inherent stochasticity of climatic processes and the artificial stochasticity of climate predictions due to scientific uncertainties. The method is worked out in some detail for the regional problem of crop production and the risks associated with global climate change, and illustrated by a case study (Kursk region of the FSU). In order to get local climatic characteristics (weather), a so-called statistical weather generator is used. One interesting finding is that the 3% risk level remains constant up to 1.0–1.1°C rise of mean seasonal temperature, if the variance does not change. On the other hand, the risk grows rapidly with increasing variance (even if the mean temperature rises very slowly). The risk approach is able to separate two problems: (i) assessment of global change impact, and (ii) decision making. The main task for the scientific community is to provide the politicians with different options; the choice of admissible (from the social point of view) critical events and the corresponding risk levels is the business of decision makers.     

Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.