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.     

The Brazilian Audit Tribunal's role in improving the federal environmental licensing process

This article describes the role played by the Brazilian Audit Tribunal (Tribunal de Contas da União — TCU) in the external auditing of environmental management in Brazil, highlighting the findings of an operational audit conducted in 2007 of the federal environmental licensing process. Initially, it records the constitutional and legal framework of Brazilian environmental licensing, describing the powers and duties granted to federal, state and municipal institutions. In addition, it presents the responsibilities of the TCU in the environmental area, comparing these with those of other Supreme Audit Institutions (SAI) that are members of the International Organization of Supreme Audit Institutions (INTOSAI).It also describes the work carried out in the operational audit of the Brazilian environmental licensing process and its main conclusions and recommendations. Finally, it draws a parallel between the findings and recommendations made in Brazil with those of academic studies and audits conducted in other countries.     

Determining subsampling effort for the development of a rapid bioassessment protocol using benthic macroinvertebrates in streams of Southeastern Brazil

The purpose of this study was to establish a subsampling procedure for benthic macroinvertebrates to aid in the development of a multimetric index to assess the biological condition of streams. Data from six streams that are considered minimally impaired were used. Subsampling was done using a device divided into 24 quadrats. The sediment from each quadrat was sorted, and all organisms were removed and identified. Richness metrics were the most affected by subsample size. Relative-abundance metrics were the most stable, proving that the sample was well distributed throughout the tray and abundance proportions were maintained. The results showed that the macroinvertebrate assemblage present in the six quadrats was similar to that present in the full sample. These analyses indicated that six quadrats, randomly designated, with a minimum of 200 collected specimens could be used in place of the full sample. In routine water management, managing time and costs are a major challenge; therefore, this type of simplification is absolutely necessary to ensure that a biomonitoring tool is useful for practical applications.     

The problem of using fixed-area subsampling methods to estimate macroinvertebrate richness: a case study with Neotropical stream data

Subsampling has been widely applied in the laboratory to process freshwater macroinvertebrate samples. Currently, many governmental agencies and research groups apply the fixed-count approach, targeting a number of individuals per sample, and at the same time keeping track of the number of quadrats (fraction of the sample) processed. However, fixed-area methods are still in use. The objective of this paper was to evaluate the reliability of macroinvertebrate taxonomic richness estimates developed from processing a standard number of subsampling quadrats (i.e., fixed-area approaches). We used a dataset from 18 tropical stream sites experiencing three different levels of human disturbance (most-, intermediate-, and least-disturbed). With 12 quadrats processed (half the sample), the collection curves started to stabilize, and for more than half of the sites studied, it was possible to sample at least 80 % of the total taxonomic richness of the sample. However, we observed that the minimum number of quadrats to achieve 80 % of taxonomic richness was strongly negatively correlated with the number of individuals collected in each site: the fewer the individuals in a sample, the greater the processed proportion of that sample needed to represent it properly. Thus our results indicate that for any given areal subsampling effort (any fixed fraction of the sample), samples with different numbers of individuals will be represented differently in terms of the proportion of the total number of taxa of the whole samples, those with greater numbers being overestimated and those with fewer numbers being underestimated. Therefore, we do not recommend the use of fixed-area subsampling methods alone if the main purpose is to measure and analyze taxonomic richness; instead, we encourage researchers to use fixed-count approaches for this purpose.     

Soil microbial characteristics at the monitoring plots on windthrow areas of the Tatra National Park (Slovakia): their assessment as environmental indicators

This study focused on the responses of soil microorganisms to different management regimes on disturbed windthrow areas. Microbial parameters potentially serving as indicators of environmental changes within a long-term monitoring of forest development after large-scale disturbance events were assessed. Basal and substrate-induced respiration, N mineralisation, catalase activity, microbial biomass as well as functional diversity based on Biolog assay were determined in soil samples from three disturbed plots and an undisturbed reference plot in the Tatra National Park (Slovakia) since 2006. A relative congruence of inter-annual trends of microbial activity indicators at all plots results from a common response of microbiota to changes of climate at the landscape level after forest stands were destroyed. While catalase activity and functional diversity proved to be useful indicators of temporal trends, microbial biomass seems to reflect different management regimes at the disturbed plots.     

Synthetic musks in environmental samples: indicator compounds with relevant properties for environmental monitoring

Synthetic musks (nitro and polycyclic musks) are a group of chemicals offering a wide range of important properties for environmental monitoring programs. They are produced as odorous chemicals and added to a wide variety of perfumes, toiletry products and other household products. As such, they are directly applied in cosmetic products or in washed textiles to the human body in considerable concentrations and accumulate owing to dermal resorption. In addition, synthetic musks also enter the environment via waste water treatment. Several polycyclic musks are chiral. By using chiral gas chromatographic methods, it is possible to determine the enantiomeric ratio and assess their bioavailability. Although an comprehensive quality assurance program must be followed during the analysis of synthetic musks in environmental samples, the determination of these compounds is not very demanding and can be carried out by a standard analytical laboratory specialising in trace analysis of organic pollutants. Owing to the pheromone-like behavior of some synthetic musks, the induction of receptors in olfactory systems should be investigated. For HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran, e.g., Galaxolide), three-dimensional structural similarities with androstenone (5 alpha-androst-16-en-3-one), a mammalian steroid pheromone, were found, which support the hypothesis of HHCB as an artificial pheromone. Owing to their environmental abundance, their relation to human activities and their potential for pheromone-like environmental behavior, synthetic musks are especially valuable as future indicator chemicals for environmental monitoring.     

Eutrophication and environmental policy in the Mediterranean Sea: a review

The Mediterranean Sea is a semienclosed basin connected with the open sea mainly through the Strait of Gibraltar. Due to the circulation pattern and the long residence time ranging between 80 and 100 years, the Mediterranean Sea is a sensitive environment to eutrophication pressures. The main body of water of the Mediterranean is characterized by very low nutrient concentrations, and therefore, the Mediterranean is classified among the most oligotrophic (very poor waters in nutrients) seas of the world's oceans. However, some coastal areas, mainly in the northern part of the basin, receive excessive loads of nutrients from sewage effluents, river fluxes, aquaculture farms, fertilizers, and industrial facilities, showing intense eutrophic phenomena with many adverse effects for the marine ecosystem and humans. Various national and international authorities, in addition to monitoring, have taken legal and administrative measures to mitigate eutrophication trends in the area. The Mediterranean environment is a good paradigm of integration of extensive legal framework, scientific knowledge, and administrative practices. The Barcelona Convention, the Mediterranean Action Plan, and European Union Directives on water quality and coastal management, together with scientific information derived from international research programs in the Mediterranean, provide a sound background for practical actions in eutrophication problems. In the present work, the problem of coastal eutrophication in the Mediterranean is reviewed in connection with public policies of the Mediterranean States based on national and international legislation and scientific knowledge on Mediterranean oceanography-ecology and actions coordinated by international bodies. These common actions and practices on coastal management are also discussed in relation to the need for sustainable development and protection of the coastal zone in the Mediterranean Sea.     

The effects of subsampling and sampling frequency on the use of surface-floating pupal exuviae to measure Chironomidae (Diptera) communities in wadeable temperate streams

Community, diversity, and biological index metrics for chironomid surface-floating pupal exuviae (SFPE) were assessed at different subsample sizes and sampling frequencies from wadeable streams in Minnesota (USA). Timed collections of SFPE were made using a biweekly sampling interval in groundwater-dominated (GWD) and surface-water-dominated (SWD) streams. These two types of stream were sampled because they support different Chironomidae communities with different phenologies which could necessitate sampling methodologies specific to each stream type. A subsample size of 300 individuals was sufficient to collect on average 85% of total taxa richness and to estimate most metrics with an error of about 1% relative to 1,000 count samples. SWD streams required larger subsample sizes to achieve similar estimates of taxa richness and metric error compared to GWD streams, but these differences were not large enough to recommend different subsampling methods for these stream types. Analysis of sample timing determined that 97% of emergence occurred from April through September. We recommend in studies where estimation of winter emergence is not important that sampling be limited to this period. Sampling frequency also affected the proportion of the community collected. To maximize the portion of the community, collected samples should be taken across seasons although no specific sampling interval is recommended. Subsampling and sampling frequency was also assessed simultaneously. When using a 300-count subsample, a 4-week sampling interval from April through September was required to collect on average 71% of the community. Due to differences in elements of the chironomid community evaluated by different studies (e.g., biological condition, phenology, and taxonomic composition), richness estimates are documented for five sampling intervals (2, 4, 6, 8, 10, and 12 weeks) and five subsample sizes (100, 200, 300, 500, and 1,000 counts). This research will enhance future studies by providing guidelines for tailoring SFPE methods to study specific goals and resources.     

The role of metadata and strategies to detect and control temporal data bias in environmental monitoring of soil contamination

It is crucial for environmental monitoring to fully control temporal bias, which is the distortion of real data evolution by varying bias through time. Temporal bias cannot be fully controlled by statistics alone but requires appropriate and sufficient metadata, which should be under rigorous and continuous quality assurance and control (QA/QC) to reliably document the degree of consistency of the monitoring system. All presented strategies to detect and control temporal data bias (QA/QC, harmonisation/homogenisation/standardisation, mass balance approach, use of tracers and analogues and control of changing boundary conditions) rely on metadata. The Will Rogers phenomenon, due to subsequent reclassification, is a particular source of temporal data bias introduced to environmental monitoring here. Sources and effects of temporal data bias are illustrated by examples from the Swiss soil monitoring network. The attempt to make a comprehensive compilation and assessment of required metadata for soil contamination monitoring reveals that most metadata are still far from being reliable. This leads to the conclusion that progress in environmental monitoring means further development of the concept of environmental metadata for the sake of temporal data bias control as a prerequisite for reliable interpretations and decisions.     

Small wonders, big future: the development of environmental nanotechnology

Nanotechnology--the engineering of atomic-scale devices and systems--is set to become one of the major industries of the 21st century. Environmental applications are emerging as a key area of interest. But alongside the benefits, there are concerns that nanotechnologies could bring new risks to the environment and human health. Are nanotechnologies friend or foe? And how can analysts contribute to the debate?     

The role of environmental and socio-demographic indicators in the analysis of land use changes in a protected area of the Natura 2000 Network: the case study of Lake Trasimeno,Umbria, Central Italy

This article sets out to analyse how and to what degree land use is linked to the physical characteristics of the territory itself, and the way in which changes in land use are determined by agricultural and socio-demographic dynamics. The study was conducted within the territorial boundaries of five municipalities surrounding Lake Trasimeno and refers to the periods 1977–2000 for land use and 1971–2001 for socio-demography data. The use of environmental, social, economic and agricultural indicators demonstrates how a mix of various indicators are useful for monitoring the changes which took place. It also shows the powerful influence that socio-demographic factors exert upon land use and landscape change.     

Evaluation of environmental fate of acetamiprid in the laboratory

The acetamiprid, a nenicotinoid insecticide, is a popular crop protection agent used in fields as well as in protected cultivation. A laboratory experiment was conditions to study the effect of light, moisture, and pH on the persistence of acetamiprid in water and soil. Dissipation half-lives of acetamiprid in water at pH 4, 7, and 9 were 6.2, 7.3, and 5.1 days, respectively, and 4.3 days under UV and sunlight conditions. Half-life in soil at three concentrations, 0.1, 1.0, and 10 μg g^?1 under different moisture regimes varied from 21.5–22.8, 15.6–22.4, 10.0–15.8 days, respectively, indicating that acetamiprid dissipated faster in submerged soil as compared to field capacity moisture and dry conditions. The leaching study showed that the possibility for leaching of acetamiprid to ground water is extremely low under normal condition of average rainfall due to compact nature soil in the field. Acetamiprid poses low risks to the ecosystem because of their rapid dissipation and low-bound residues in the environment.