Towards a sampling strategy for the assessment of forest condition at European level: combining country estimates

A correct characterization of the status and trend of forest condition is essential to support reporting processes at national and international level. An international forest condition monitoring has been implemented in Europe since 1987 under the auspices of the International Co-operative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP Forests). The monitoring is based on harmonized methodologies, with individual countries being responsible for its implementation. Due to inconsistencies and problems in sampling design, however, the ICP Forests network is not able to produce reliable quantitative estimates of forest condition at European and sometimes at country level. This paper proposes (1) a set of requirements for status and change assessment and (2) a harmonized sampling strategy able to provide unbiased and consistent estimators of forest condition parameters and of their changes at both country and European level. Under the assumption that a common definition of forest holds among European countries, monitoring objectives, parameters of concern and accuracy indexes are stated. On the basis of fixed-area plot sampling performed independently in each country, an unbiased and consistent estimator of forest defoliation indexes is obtained at both country and European level, together with conservative estimators of their sampling variance and power in the detection of changes. The strategy adopts a probabilistic sampling scheme based on fixed-area plots selected by means of systematic or stratified schemes. Operative guidelines for its application are provided.     

Ecological assessments of surface water bodies at the river basin level: a case study from England

Ecological assessments of surface water bodies are essential in order to evaluate the level of degradation in freshwater ecosystems and to address the subsequent decline in services they provide. These assessments cover multiple aspects of the aquatic environment, particularly biological elements due to their ability to respond to all pressures within an ecosystem. Such assessments can enable the identification of the multiple pressures which threaten water bodies, facilitating sustainable decisions regarding their management to be identified. Here, the design requirements of the networks which facilitate ecological assessments are presented. A river basin district in England is used as a case study to investigate the number of elements monitored, the number of failing elements and the relationship between failing elements. Findings demonstrate the value of ensuring that monitoring networks are risk based and appropriately designed to meet their objectives. This therefore requires that monitoring is not only for the communicating of compliance but also for use iteratively so that the design of monitoring networks and ultimately management can be continually improved.     

Development of an efficient and sensitive analytical method for the determination of copper at trace levels by slotted quartz tube atomic absorption spectrometry after vortex-assisted dispersive liquid-liquid microextraction in biota and water samples using a novel ligand

This study describes the determination of trace levels of copper by slotted quartz tube atomic absorption spectrometry after dispersive liquid-liquid microextraction. A ligand synthesized from the reaction of salicylaldehyde and 1-naphthylamine was used to form coordinate copper complex prior to extraction. All parameters that influence the output of complex formation, extraction, and instrumental measurement were optimized to enhance the absorbance signal of copper. Under the optimum conditions, about 104-fold enhancement in sensitivity was recorded over the conventional flame atomic absorption spectrometer, corresponding to a 0.51 ng/mL detection limit. The percent relative standard deviation calculated for the lowest concentration (4.8%) indicated high precision for the experimental procedure. Accuracy and applicability of the optimum method were determined by performing spiked recovery tests on urine, lake water, and mineral water samples. Satisfactory recovery results were obtained between 82.2 and 106.3% at four different concentrations. Matrix matching method was also performed to increase the accuracy of quantification, and the percent recovery calculated for 175 ng/mL was 105.14%.     

Comparison of a matrix solid phase dispersion and a classical extraction method for the determination of chlorinated pesticides in fish muscle

A new multiresidue extraction technique was used to determine incurred chlorinated hydrocarbon pesticide residues in various fish species sampled at 2 locations along the Tensas River in Louisiana. Residue levels of total DDT (combined DDT, DDE, and DDD levels) in fish muscle fillets from paired samples ranged from 0.2 to 3.9 ppm on a wet weight basis. These findings were compared to those of another laboratory that used a different protocol to isolate the residues from the fish muscle fillets. This latter protocol typifies the more complicated, time-consuming protocols used by governmental agencies for screening purposes. Results demonstrated that the new extraction technique reduced analysis time, solvent waste, and cost per sample without affecting the quality of residue detection and measurement.     

Development of a novel passive sampling system for the time-averaged measurement of a range of organic pollutants in aquatic environments

A new sampling system has been developed for the measurement of time-averaged concentrations of organic micropollutants in aquatic environments. The system is based on the diffusion of targeted organic compounds through a rate-limiting membrane and the subsequent accumulation of these species in a bound, hydrophobic, solid-phase material. It provides a novel and robust solution to the problem of monitoring in situations where large temporal fluctuations in pollutant levels may occur. Accumulation rates are regulated by choice of diffusion-limiting membrane and bound solid-phase material and have been found to be dependent on the physico-chemical properties of individual target analytes. Two separate prototype systems are described: one suitable for the sampling of non-polar organic species with log octanol/water partition coefficient (log P) values greater than 4, the other for more polar species with log P values between 2 and 4. Both systems use the same solid-phase material (47 mm C18 Empore disk) as a receiving phase but are fitted with different rate-limiting membrane materials (polysulfone for the polar and polyethylene for the non-polar analytes). The two systems complement each other and together can be used for sampling a wider range of organic analytes than generally possible using current passive sampling techniques. Calibration data are presented for both devices. In each case, linear uptake kinetics were sustained, under constant conditions, for deployment periods of between 1 and 9 days. The effects of water temperature and turbulence on sampling rates have been quantitatively assessed. The performance of the system was further investigated by means of field exposures for one and two weeks in marine environments where calibrated samplers were used to determine the time-averaged concentrations of the polar biocides diuron and irgarol 1051. The quantitative results obtained using the passive sampler were compared with those obtained using spot sampling.     

Continuous flow methods for evaluating the response of a copper ion selective electrode to total and free copper in seawater

This work describes the development of an instrument for measuring free and total copper in seawater by continuous flow analysis (CFA) with an Orion copper (II) ion selective electrode (CuISE). Sample analysis times are reduced considerably by using an extrapolation technique based on the fitting of an empirical mathematical expression to the electrode time-response curve enabling a prediction of the final equilibrium potential. CuISE measurements in seawater samples containing nanomolar levels of total copper can be very time consuming, and this predictive approach significantly reduces sample analysis time, and improves sample throughput. The time taken to measure pCu in seawater to a precision of +/- 0.1, using conventional potentiometry, varies considerably depending on the condition of the electrode membrane but can be reduced by a factor of 3-6 (typically from 60 to 10 min) by using the extrapolation technique in conjunction with CFA. Details are given of the protocols used for preconditioning the CuISE. The system can be used as a portable instrument for field measurements or for shipboard measurements of free copper in seawater. Extrapolated equilibrium potentials are within +/- 0.5 mV of true steady state values.     

Evaluation of sediment quality guidelines derived using the screening-level concentration approach for application at uranium operations in Saskatchewan,Canada

Sediment quality guidelines (SQGs) can be derived using different approaches and are commonly used in environmental management, reclamation, and risk assessment. The screening-level concentration (SLC) approach has been used in Ontario, Canada, to derive lowest effect levels (LELs) and severe effect levels for use as SQGs. This approach was adopted by the Canadian Nuclear Safety Commission (CNSC) to set guidelines for metals (As, Cr, Cu, Pb, Mo, Ni, Se, U, and V) and radionuclides (Ra-226, Pb-210, and Po-210) in sediment at northern Saskatchewan uranium mining and milling operations. The SLC approach is based on total metal and radionuclide concentrations in sediment, and corresponding benthic community composition data for a specific sampling site. In this study, sediment chemistry (total metals and radionuclides) and benthic community data from northern Saskatchewan uranium operations were compiled and examined. Results indicate that the CNSC-derived SQGs had limited relationships to observed effects, or lack thereof, on benthic invertebrate communities near uranium operations in Saskatchewan. The LELs were found to correctly align with effects at 95% of the sites that had effects, on a general basis, but on an element-specific basis many of the elements had concentrations at effect sites below their LELs. Furthermore, concentrations of the evaluated elements exceeded at least one LEL at 60% of the no-effect sites. The high number of exceedences of LELs at reference and no-effect sites (false-positives) calls to question the appropriateness of the CNSC-derived SQGs. It is suggested that alternatives to the SLC approach be explored.     

On the intensity and type transition of land use at the basin scale using RS/GIS: a case study of the Hanjiang River Basin

The purpose of this study is to investigate the land use intensity and land use change type at the basin scale in the middle and lower reaches of the Hanjiang River Basin (in Hubei Province, China) by combining the Landsat TM images in 1995 and 2000 with the land use database (in scale 1:10,000) and relative data. In this study, the basic data is acquired from the interpretation of remote sensing (RS) images. The intensity of land use and the rate of change in double-directions of land use dynamics are calculated with the support of software ARC/INFO. The intensity of land use is indicated by the intensity coefficient of land use, and the transition of land use types is quantified as the rate of change in double-direction of land use types and also expressed as the transition matrix of land use types. The results are expressed in space by Geographic Information System (GIS) software. Results of this study show that (1) the intensity of land use is high in the study region, the intensity coefficients of land use in 1995 and 2000 are 260.025 and 290.526, respectively, and the intensity of development and utilization of land is trend to increscent; and (2) the rate of land use change in double directions in the whole study region is 0.52 with great spatial variation and the differentiation of land use types. In the differentiation of land use types, the unutilized land (with the rate to 4.391) is developed fast, the grassland (with 2.836) and water area (with 1.664) are disturbed severely, and these changes will influence the eco-environment in the Hanjiang River Basin and all the Yangtze Basin. The rates of the farmland and the woodland are 0.424 and 0.344, respectively, meaning that the fundamentals of regional human-environmental system are relative stable. With this study, we can conclude that (1) the patterns of land use are increasingly changing in the study region, the environmental impacts are escalated on this stage, and the further outcomes are destined to change the stability of the regional human–environmental system; and (2) the most useful method to study the present land use and its change is through the use of the RS/GIS with the land use database (in scale 1:10,000).     

Estimation of the contributions of long range transported aerosol in East Asia to carbonaceous aerosol and PM concentrations in Seoul, Korea using highly time resolved measurements: a PSCF model approach

The contributions of long range transported aerosol in East Asia to carbonaceous aerosol and particulate matter (PM) concentrations in Seoul, Korea were estimated with potential source contribution function (PSCF) calculations. Carbonaceous aerosol (organic carbon (OC) and elemental carbon (EC)), PM(2.5), and PM(10) concentrations were measured from April 2007 to March 2008 in Seoul, Korea. The PSCF and concentration weighted trajectory (CWT) receptor models were used to identify the spatial source distributions of OC, EC, PM(2.5), and coarse particles. Heavily industrialized areas in Northeast China such as Harbin and Changchun and East China including the Pearl River Delta region, the Yangtze River Delta region, and the Beijing-Tianjin region were identified as high OC, EC and PM(2.5) source areas. The conditional PSCF analysis was introduced so as to distinguish the influence of aerosol transported from heavily polluted source areas on a receptor site from that transported from relatively clean areas. The source contributions estimated using the conditional PSCF analysis account for not only the aerosol concentrations of long range transported aerosols but also the number of transport days effective on the measurement site. Based on the proposed algorithm, the condition of airmass pathways was classified into two types: one condition where airmass passed over the source region (PS) and another condition where airmass did not pass over the source region (NPS). For most of the seasons during the measurement period, 249.5-366.2% higher OC, EC, PM(2.5), and coarse particle concentrations were observed at the measurement site under PS conditions than under NPS conditions. Seasonal variations in the concentrations of OC, EC, PM(2.5), and coarse particles under PS, NPS, and background aerosol conditions were quantified. The contributions of long range transported aerosols on the OC, EC, PM(2.5), and coarse particle concentrations during several Asian dust events were also estimated. We also investigated the performance of the PSCF results obtained from combining highly time resolved measurement data and backward trajectory calculations via comparison with those from data in low resolutions. Reduced tailing effects and the larger coverage over the area of interest were observed in the PSCF results obtained from using the highly time resolved data and trajectories.     

Migration of As, Hg, Pb, and Zn in arroyo sediments from a semiarid coastal system influenced by the abandoned gold mining district at El Triunfo, Baja California Sur, Mexico

Extensive waste deposits (tailings) and ash from the ignition oven of the abandoned gold mine of mining district El Triunfo (MD-ET) in Baja California Sur, Mexico have released trace elements into the sediments of the Hondo-Las Gallinas-El Carrizal arroyo, which connects to the Pacific Ocean through an evaporitic basin. Migration of these elements through the arroyo is mainly caused by winds or tropical hurricanes that occur sporadically during the summer and cause the otherwise dry arroyo to overflow. To evaluate the concentration and distribution of the elements As, Hg, Pb, and Zn along the 48 km arroyo, surface sediments were collected from 26 sites, ranging from close to the MD-ET to the mouth of the arroyo at the Pacific Ocean. Concentrations in tailings and ash were for As 8890 and 505?000 mg kg(-1); for Hg 0.336 and 54.9 mg kg(-1); for Pb 92,700 and 19,300 mg kg(-1); and for Zn 49,600 and 1380 mg kg(-1). The average of the Normalized Enrichment Factor (Av-NEF) in surface sediments, calculated using background levels, indicates that the sediments are severely contaminated with As and Zn (Av-NEF = 22), Pb (Av-NEF = 24) and with a moderate contamination of Hg (Av-NEF = 7.5). The anthropogenic influence of those elements is reflected in the arroyo sediments as far as 18 km away from the MD-ET, whereas the samples closest to the discharge into the Pacific Ocean show a natural to moderate enrichment for As and Zn and low or no enrichment for Hg and Pb. A principal components analysis identified four principal components that explained 90% of the total variance. Factor 1 was characterized by a high positive contribution of the anthropogenic source elements, especially As, Pb, and Zn (37%), whereas Factor 2 was strongly correlated with the oxy-hydroxides of Fe and Mn (27%). Factor 3 was correlated with Li (16%) and Factor 4 with Al (10%), which indicates more than one source of lithogenic composition, though they played a minor role in the distribution of the elements.     

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.     

Development of a new method for the determination of residues of the neonicotinoid insecticide imidacloprid in juvenile chinook (Oncorhynchus tshawytscha) using ELISA detection

The neonicotinoid insecticide imidacloprid (IMI) has been proposed as an alternative to carbaryl for controlling indigenous burrowing shrimp on commercial oyster beds in Willapa Bay and Grays Harbor, Washington. A focus of concern over the use of this insecticide in an aquatic environment is the potential for adverse effects from exposure to non-target species residing in the Bay, such as juvenile Chinook (Oncorhynchus tshawytscha) and cutthroat trout (O. clarki). Federal registration and State permiting approval for the use of IMI will require confirmation that the compound does not adversely impact these salmonids following field applications. This will necessitate an environmental monitoring program for evaluating exposure in salmonids following the treatment of beds. Quantification of IMI residues in tissue can be used for determining salmonid exposure to the insecticide. Refinement of an existing protocol using liquid-chromatography mass spectrometry (LC-MS) detection would provide the low limits of quantification, given the relatively small tissue sample sizes, necessary for determining exposure in individual fish. Such an approach would not be viable for the environmental monitoring effort in Willapa Bay and Grays Harbor due to the high costs associated with running multiple analyses, however. A new sample preparation protocol was developed for use with a commercially available enzyme-linked immunosorbent assay (ELISA) for the quantification of IMI, thereby providing a low-cost alternative to LC-MS for environmental monitoring in Willapa Bay and Grays Harbor. Extraction of the analyte from the salmonid brain tissue was achieved by Dounce homogenization in 4.0 mL of 20.0 mM Triton X-100, followed by a 6 h incubation at 50-55 °C. Centrifugal ultrafiltration and reversed phase solid phase extraction were used for sample cleanup. The limit of quantification for an average 77.0 mg whole brain sample was calculated at 18.2 μg kg(-1) (ppb) with an average recovery of 79%. This relatively low limit of quantification allows for the analysis of individual fish. Using controlled laboratory studies, a curvelinear relationship was found between the measured IMI residue concentrations in brain tissue and exposure concentrations in seawater. Additonally, a range of IMI brain residue concentrations was associated with an overt effect; illustrating the utility of the IMI tissue residue quantification approach for linking exposure with defined effects.     

Influence of reagent purity on the ion chromatographic determination of bromate in water using 3,3'-dimethoxybenzidine as a prochromophore for photometric detection

Variable availability of the purified dihydrochloride salt of 3,3'-dimethoxybenzidine (DMB; ortho-dianisidine) led us to investigate the effects of reagent purity on the analytical results obtained when this reagent is used in the photometric determination of the disinfection byproduct bromate. After analyte ions are separated by ion chromatography, a solution of DMB (post-column reagent) is added to the eluate and the DMB is oxidized, thereby producing a chromophore detected by its absorbance. Although some commercial products of undefined grade performed well, others did not. Variability was also observed between lots of purified material. Sensitivity at low concentrations (< 5 micrograms L-1 BrO3-) varied by a factor of up to 10. In some cases, the lower limit of detection for photometric detection was greater than that obtained using conductivity detection, as high as 5-7 micrograms L-1 BrO3-. An impurity or several impurities are suspected to be responsible for deviations from linearity at low analyte concentrations. This investigation underscores the need for ensuring reagent purity in environmental analyses. Ideally, chemical manufacturers will meet the needs of analytical chemists who test potable water and begin producing a high grade material in sufficient quantities to meet monitoring requirements. The establishment of third-party standards for a spectrophotometric grade of DMB.2HCl would be helpful in ensuring that a variety of manufacturers could supply products of uniformly high quality that would be suitable for the measurement of bromate in public drinking water supplies.     

Holistic approach for quantification and identification of pollutant sources of a river basin by analyzing the open drains using an advanced multivariate clustering

Global scarcity of freshwater has been gearing towards an unsustainable river basin management and corresponding services to the humans. It needs a holistic approach, which exclusively focuses on effective river water quality monitoring and quantification and identification of pollutant sources, in order to address the issue of sustainability. These days, rivers are heavily contaminated due to the presence of organic and metallic pollutants released from several anthropogenic sources, such as industrial effluents, domestic sewage, and agricultural runoff. It is astonishing to note that even in many developing countries, most of these contaminants are carried through open drains, which enter river premises without proper treatment. Such practice not only devastates riverine ecosystem but also gives rise to deadly diseases, such as minimata and cancer in humans. Considering these issues, the present study develops a novel approach towards simultaneous identification of major sources of pollution in the rivers, along with critical pollutants and locations using an advanced hierarchical cluster and multivariate statistical analysis. A systematic approach has been developed by agglomerating both R-mode and Q-mode analysis, which develops monoplots, two-dimensional biplots, rotated component matrices, and dendrograms (using “SPSS” and “Analyse It” software) to reveal relationships among various quality parameters to identify the pollutant sources along with clustering of critical sampling sites and pollutants. A case study of the Ganges River Basin of India has been considered to demonstrate the efficacy and usefulness of the model by analyzing 85 open drains. Both organic and metallic pollutants are analyzed simultaneously as well as separately to get a holistic understanding of all the relationships and to broaden the perspective of water characterization. Results provide a comprehensive guidance to the policy makers and water managers to optimize corrective efforts, minimize further damage, and improve the water quality condition to ensure sustainable development of the river basin.     

Brown trout as a sentinel organism for organic pollution in the field using catalytic and immunochemical assays of cytochrome P-450 1A

The measurement in some living organisms of adequate biomarkers (e.g. cytochrome P-450) to assess the organic pollution in freshwater ecosystems is well established. However, the sensitivity of this approach depends on the analytical measurement method employed and on the chosen living organism for the biomonitoring. Three analytical methods were compared for measuring cytochrome P-450 1A levels in wild brown trout (Salmo trutta): a catalytic one, based on measurement of the ethoxyresorufin-O-deethylase (EROD) activity, and two immunochemical methods, namely, enzyme-linked immunosorbent assay (ELISA) and western blotting. The P-450 1A levels in those animals from a river located in an industrialized area (Trubia River, Northern Spain) and also from individuals living in a low-contamination reference area have been studied. Significant differences (Mann-Whitney U-test, P < 0.01) between rivers were found (ELISA and EROD assays), with the values for Trubia river being similar to those observed in laboratory experiments with well known P-450 1A inducers. However, no significant differences were observed in terms of sex and age. Western blot analysis confirmed the presence of a single band of 56 kDa (corresponding with P-450 1 A protein) in microsomes of fish caught in the Trubia river. On the other hand, and associated with the chemical analysis of PAHs in the waters of both rivers by SPME-GC-MS, high levels of naphthalene (P-450 1A inducer) in the contaminated river were found. In brief, a wide difference between basal levels and P-450 1A induction levels could be detected in trout living in natural field conditions using both EROD activity assay and immunochemical methods. Therefore, brown trout could constitute a good sentinel organism to biomonitor the exposure to PAHs in rivers using P-450 1A measurements.