A comparative study on various statistical techniques predicting ozone concentrations: implications to environmental management

The objective of the present work is to compare various techniques for modeling the dependence of the tropospheric ozone concentrations on several meteorological and pollutant parameters. The study focuses on two different sites in the metropolitan area of Athens, Greece; one in the city centre and another one in the suburbs. It is found that although simple Linear Regression Analysis fails to construct accurate equations due to the existence of multicollinearity among the independent variables, still various combinations of a Multivariate Method (PCA) and Stepwise Regression Analysis manage to produce equations free of the multicollinearity issue. The derived formulas are validated and prove to have R(2) values in the order of 0.8 approximately. However, the equations are found to be unsuccessful in case of severe episodes. For this reason, a new procedure is followed for estimating the ozone values in case of episodes exclusively. The new R(2) value is estimated to be 0.9, approximately.     

Response of macroinvertebrate communities to remediation-simulating conditions in Pennsylvania streams influenced by acid mine drainage

We compared naturally alkaline streams with limestone lithology to freestone streams with and without acid mine drainage (AMD) to predict benthic macroinvertebrate community recovery from AMD in limestone-treated watersheds. Surrogate-recovered (limestone) and, in many cases, freestone systems had significantly higher macroinvertebrate densities; diversity; taxa richness; Ephemeroptera, Plecoptera, and Trichoptera (EPT) taxa; EPT/chironomid ratios; scraper/collector-gatherer ratios; herbivores; collector-filterers; and scrapers. AMD-influenced systems had significantly greater numbers of Diptera and collector-gatherers. An entire trophic level (herbivores) was "restored" in surrogate-recovered streams, which also showed greater trophic specialization. Indicator analysis identified seven taxa (within Crustacea, Diptera, Nematoda, Trichoptera, and Ephemeroptera) as significant indicators of limestone systems and six taxa (within Ephemeroptera, Plecoptera, Tricoptera, Coleoptera, and Mollusca) as significant freestone indicators, all useful as biological indicators of recovery from AMD.     

Ecotoxicological assessment of acid mine drainage: electrophysiological changes in earthworm (Aporrectodea caliginosa) and aquatic oligochaete (Lumbriculus variegatus)

Ecological health of 15 sites in two mining areas on the West Coast of the South Island, New Zealand, was assessed using a non-invasive electrophysiological technique. The conduction velocity (CV) changes in the medial giant fibres (MGF) of the terrestrial earthworm Aporrectodea caliginosa were measured on days 0, 1, 2, 4, 7, 14, and 21 following exposure to soil and/or sediment from six acid mine drainage (AMD) sites, and aquatic oligochaete Lumbriculus variegatus at 0, 3, 6, and 24 h following exposure to water from 14 AMD sites. The colour of the soil/sediments varied from red-brown to black with pH ranging from 4.46 to 7.37. The colour of AMD water samples varied from clear, black, brown to orange, and the pH ranged from 2.99 to 7.66. The CV decreased progressively in A. caliginosa exposed to most soil and sediment samples from the AMD sites (compared with controls exposed to soil from an organic farm) and this was most evident in measurements taken at 7 days. Based on the CV measurements taken on day 7, sites 3 > 2 > 1 were significantly (P < 0.05) the most toxic to earthworms. The CV of L. variegatus exposed to AMD water sampled from many sites also decreased progressively and this was significantly lower than the controls in the measurements taken at 24 h from sites 3 > 9 > 7 > 11. It is proposed that MGF CV in A. caliginosa and L. variegatus worms can be used as a non-invasive, sensitive, biomarker to monitor the toxicity of AMD sites.     

Soil solution extraction techniques for microbial ecotoxicity testing: a comparative evaluation

The suitability of two different techniques (centrifugation and Rhizon sampler) for obtaining the interstitial pore water of soil (soil solution), integral to the ecotoxicity assessment of metal contaminated soil, were investigated by combining chemical analyses and a luminescence-based microbial biosensor. Two different techniques, centrifugation and Rhizon sampler, were used to extract the soil solution from Insch (a loamy sand) and Boyndie (a sandy loam) soils, which had been amended with different concentrations of Zn and Cd. The concentrations of dissolved organic carbon (DOC), major anions (F- , CI-, NO3, SO4(2-)) and major cations (K+, Mg2+, Ca2+) in the soil solutions varied depending on the extraction technique used. Overall, the concentrations of Zn and Cd were significantly higher in the soil solution extracted using the centrifugation technique compared with that extracted using the Rhizon sampler technique. Furthermore, the differences observed between the two extraction techniques depended on the type of soil from which the solution was being extracted. The luminescence-based biosensor Escherichia coli HB101 pUCD607 was shown to respond to the free metal concentrations in the soil solutions and showed that different toxicities were associated with each soil, depending on the technique used to extract the soil solution. This study highlights the need to characterise the type of extraction technique used to obtain the soil solution for ecotoxicity testing in order that a representative ecotoxicity assessment can be carried out.     

Attenuation of dissolved metals in neutral mine drainage in the Zambian Copperbelt

Behaviour of metals like Cu and Co was studied in nearly neutral (pH ?? 6.4) mine drainage seepage in a stream downgradient of a tailing dam at Chambishi site in the Copperbelt of Zambia. They are attenuated by precipitation of ferruginous ochres that incorporate significant quantities of metals. Using chemical analysis, X-ray powder diffraction and M?ssbauer spectroscopy, we show that the ochres are composed mostly of amorphous ferric hydroxide. Close to the seepage face, the total Fe content of ochres increases due to precipitation of amorphous ferric hydroxide, but total Fe in sediment decreases further downstream. The stream then flows through wetland (dambo) where the remaining fraction of metals is removed. During rainy periods, increased flow rate may result in re-suspension of ochres, increasing thus the mobility of metals. Major ions like sulphate are conservative at the start of the dry period (May), but gypsum may probably precipitate later at the end of the dry period. Sequential extractions of bulk sediments indicate that Mn behaves differently to Fe, with a trend of increasing Mn with distance from the tailing dam. There is much more Fe than Mn in residual (Aqua Regia) fraction, indicating that amorphous ferric hydroxides are transformed to more crystalline phases deeper in sediment. Environmental impact of mine drainage is relatively limited due to its neutral character.     

Determination and evaluation of hexavalent chromium in power plant coal combustion by-products and cost-effective environmental remediation solutions using acid mine drainage

The chromium species leaching from a coal combustion fly ash landfill has been characterized as well as a novel approach to treat leachates rich in hexavalent chromium, Cr(VI), by using another natural waste by-product, acid mine drainage (AMD), has been investigated during this study. It is observed that as much as 8% (approximately 10 microg g(-1) in fly ash) of total chromium is converted to the Cr(VI) species during oxidative combustion of coal and remains in the resulting ash as a stable species, however, it is significantly mobile in water based leaching. Approximately 1.23 +/- 0.01 microg g(-1) of Cr(VI) was found in the landfill leachate from permanent deposits of aged fly ash. This study also confirmed the use of AMD, which often is in close proximity to coal combustion by-product landfills, is an extremely effective and economical remediation option for the elimination of hexavalent chromium in fly ash generated leachate. Speciated isotope dilution mass spectrometry (SIDMS), as described in EPA Method 6800, was used to analytically evaluate and validate the field application of the ferrous iron and chromate chemistry in the remediation of Cr(VI) runoff.     

Effects of roof and rainwater characteristics on copper concentrations in roof runoff

Copper sheeting is a common roofing material used in many parts of the world. However, copper dissolved from roof sheeting represents a source of copper ions to watersheds. Researchers have studied and recently developed a simple and efficient model to predict copper runoff rates. Important input parameters include precipitation amount, rain pH, and roof angle. We hypothesized that the length of a roof also positively correlates with copper concentration (thus, runoff rates) on the basis that runoff concentrations should positively correlate with contact time between acidic rain and the copper sheet. In this study, a novel system was designed to test and model the effects of roof length (length of roof from crown to the drip edge) on runoff copper concentrations relative to rain pH and roof angle. The system consisted of a flat-bottom copper trough mounted on an apparatus that allowed run length and slope to be varied. Water of known chemistry was trickled down the trough at a constant rate and sampled at the bottom. Consistent with other studies, as pH of the synthetic rainwater decreased, runoff copper concentrations increased. At all pH values tested, these results indicated that run length was more important in explaining variability in copper concentrations than was the roof slope. The regression equation with log-transformed data (R ² = 0.873) accounted for slightly more variability than the equation with untransformed data (R ² = 0.834). In log-transformed data, roof angle was not significant in predicting copper concentrations.     

Size distribution in ultraphytoplankton: A comparative analysis of counting methods

Water samples taken at three depth layers from the offshore oligotrophic Cretan Sea were analyzed for ultraphytoplankton size fractionation using different methods: (a) sequential filtration on filters of pore size 5, 1 and 0.2 m, (b) separate filtration using filters 5 and 0.2 m as well as 1 and 0.2 m and (c) direct filtration on 0.2 m filters after staining of the samples with DAPI. Total abundance of photosynthetic organisms as well as the abundance of different groups such as flagellates and cyanobacteria measured by means of sizing after DAPI staining were significantly higher than those obtained by the other methods. This indicates that although there were no significant differences between the estimates provided by the separate and sequential filtration, both these methods underestimated total abundance by at least 25–50%. The estimates for the size fractions were also found to range from relatively imprecise to completely unreliable depending on the group and the size range. Although size fractionation through direct observation after staining largely depends on the expertise of the observer, this study suggests that it may provide more informative estimates than the other two methods. Although it is difficult to generalize the results of this study in a global context, the paper provides strong indications on the limitations of the sequential and separate methods for size fractionation of photosynthetic organisms and implies that their results are likely to be less accurate than is presently believed.     

Use of the Multispecies Freshwater Biomonitor to assess behavioral changes of Poecilia reticulata (Cyprinodontiformes: Poeciliidae) and Macrobrachium lanchesteri (Decapoda: Palaemonidae) in response to acid mine drainage: laboratory exposure

The behavioral responses of guppy Poecilia reticulata (Poeciliidae) and prawn Macrobrachium lanchesteri (Palaemonidae) individuals exposed to acid mine drainage (AMD) were monitored online in the laboratory with a Multispecies Freshwater Biomonitor? (MFB). These responses were compared to those to reference water acidified to the respective pH values (ACID). Test animals in the juvenile stage were used for both species and were exposed to AMD and ACID for 24 hours. The stress behaviors of both test animals consisted mainly of decreased activity in AMD and increased activity in ACID, indicating that the metals in the AMD played a role as a stress factor in addition to pH. The locomotor activity levels of guppies and prawns for the ACID treatment were higher than the locomotor activity levels for the AMD treatment with increasing pH value. For guppies, significant differences were observed when specimens were exposed to AMD and ACID at pH 5.0 and 6.0; the percentage activities were only 16% and 12%, respectively, for AMD treatment, whereas for ACID treatment, the percentage activities were 35% and 40%, respectively, similar to the value of 36% for the controls. Similar trends were also observed for prawns, for which the percentage activities were only 6% and 4%, respectively, for AMD treatment, whereas for ACID treatment, the percentage activities were 31% and 38%, respectively, compared to 44% in the controls. This study showed that both species are suitable for use as indicators for ecotoxicity testing with the MFB.     

Metal accumulation in the tissues of grass carps (Ctenopharyngodon idellus) from fresh water around a copper mine in Southeast China

Mining effluents are the main source of metals in the surrounding aquatic environment. The mining district of Purple Mountain has a history of copper mining for more than 30 years, but there is limited investigation of metal bioaccumulation in the aquatic creatures from the Tingjiang river catchment affected by the mining activities. In this study, we collected grass carps (Ctenopharyngodon idellus) from four sites, and analyzed the accumulation of chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd), mercury (Hg), and lead (Pb) in ten tissues (scale, skin, muscle, gill, liver, kidney, fish maw, heart, stomach, and intestine) of the fish samples. Among all tissue samples, the highest concentrations (micrograms per gram wet weight) of Ni (0.263), Cu (69.2), Zn (84.0), As (0.259), Cd (0.640), Hg (0.051), and Pb (0.534) were noted in the liver, gill, and kidney tissues, whereas the highest concentrations of Cr (0.356) and Mn (62.7) were detected in the skin and intestine, respectively. These results gave a better understanding of the variability of metals distribution in different fish tissues. In comparison with the sample sites, metals (especially Mn, Cu, Zn, Ni, and Pb) in liver, gill, kidney, stomach, and intestine showed more inter-site differences than other tissues. The inter-site differences also revealed that site 1 and 2 increased fish uptake of Cu, Zn, Ni, and Pb, which may indicate that the copper mine and urban effluents contributed to high levels of these metals in aquatic environments in site 1 and 2. A potential food safety issue may emerge depending on the mining activities in this region because some metals in a few tissue samples exceeded the guideline values for human consumption of fish.     

Evaluation of the impacts of mine drainage from a coal waste pile on the surrounding environment at Smolnica, southern Poland

Mine drainage impacts from a coal waste pile at Smolnica, Poland have been monitored. Groundwater in an unconfined aquifer downgradient from the pile has near-neutral pH, but high concentrations of sulfate (up to 3,827 mg/l), chloride (up to 903 mg/l), and sodium (up to 2,606 mg/l). Concentrations of iron and manganese are elevated only locally, and concentrations of other metals are low. The behavior of sulfate seems to be conservative in the downgradient aquifer, and gypsum may only be precipitating locally. Concentrations of iron and manganese seem to be controlled by the precipitation of ferric oxide and hydroxides and rhodochrosite, respectively. Complete neutralization of mine drainage by carbonates is consistent with high concentrations of calcium (up to 470 mg/l) and magnesium (up to 563 mg/l) and also with high strontium concentrations of up to 3.08 mg/l, observed in groundwater downgradient from the pile. Hydraulic head profiles at two sites within the river bottom sediments indicate upward flow toward the river with large local differences in groundwater recharge. Water chemistry profiles in the river bottom sediments and geochemical modeling suggest conservative behavior of Na, Cl, and SO₄ and precipitation of Fe and Mn at the groundwater/river water interface. Mine drainage enters the Bierawka River and causes increasing sulfate concentrations. In contrast, concentrations of sodium and chloride in the Bierawka River decrease downgradient from the pile because water in the river upgradient from the pile is already highly contaminated by these species from the discharge of mining waters. Concentrations of Fe and Mn in the river water are low, as a consequence of the precipitation of Fe and Mn oxide and hydroxides. Direct geochemical modeling was able to reproduce measured concentrations of conservative species (e.g., Na, Cl, and SO₄), but errors for metals and Ba were relatively large. In addition, calculated P_CO2 values in the river water are very high, suggesting that equilibrium with atmospheric P_CO2 and P_O2 has not been reached, and at least some reactions should be modeled as kinetic processes. High concentrations of Na, Cl, and SO₄ contribute to the contamination of the Odra River, which is joined by the Bierawka River farther downgradient, thus limiting the use of river water for recreation and other purposes.     

Multivariate analysis of heavy metals concentrations in river estuary

Multivariate statistical techniques such as multivariate analysis of variance (MANOVA) and discriminant analysis (DA) were applied for analyzing the data obtained from two rivers in the Penang State of Malaysia for the concentration of heavy metal ions (As, Cr, Cd, Zn, Cu, Pb, and Hg) using a flame atomic absorption spectrometry (F-AAS) for Cr, Cd, Zn, Cu, Pb, As and cold vapor atomic absorption spectrometry (CV-AAS) for Hg. The two locations of interest with 20 sampling points of each location were Kuala Juru (Juru River) and Bukit Tambun (Jejawi River). MANOVA showed a strong significant difference between the two rivers in terms of heavy metal concentrations in water samples. DA gave the best result to identify the relative contribution for all parameters in discriminating (distinguishing) the two rivers. It provided an important data reduction as it used four parameters (Zn, Pb, Cd and Cr) affording 100% correct assignations. Results indicated that the two rivers were different in terms of heavy metals concentrations in water, and the major difference was due to the contribution of Zn. A negative correlation was found between discriminate functions (DF) and Cr and As, whereas positive correlation was exhibited with other heavy metals. Therefore, DA allowed a reduction in the dimensionality of the data set, delineating a few indicator parameters responsible for large variations in heavy metal concentrations. Correlation matrix between the parameters exhibited a strong evidence of mutual dependence of these metals.     

Permeability of hair to cadmium,copper and lead in five species of terrestrial mammals and implications in biomonitoring

The capacity of mammal hair to absorb toxic metals and its utility in biomonitoring has been broadly studied. Though these metal-binding properties has generally been attributed to the sulphur contained in cysteine, an amino acid that forms part of keratin, there are not many experimental studies that analyze the role of sulphur in the external deposition of potentially toxic metallic elements in order to better understand the potential of hair in biomonitoring and generate better tools for differentiating between internal and external deposition of contaminants. In this study, an experimental analysis is carried out using a scanning electron microscope on hairs of five terrestrial mammal species (Peromyscus furvus, P. maniculatus, Glossophaga soricina, Artibeus jamaicensis and Marmosa mexicana) treated with cadmium, copper and lead salts. We quantified absorbed metals as well as natural elements of the hair by energy dispersive X-ray spectroscopy (EDS) to analyze using simple statistics the role of sulphur in the absorption Cd, Cu and Pb. Given the lack of studies comparing the mechanisms of deposition of metal elements among different orders of Class Mammalia, external morphology was considered to be an important factor in the deposition of metallic particles of Cd, Cu and Pb. Bat species (Glossophaga soricina, Artibeus jamaicensis) showed a high concentration of particles in their scales, however, no between-species differences in metal absorption were observed, and during the exogenous deposition metal particles do not permeate the medulla. These results suggest that the sulphur in hair itself cannot bind metals to hair cuticle and that hair absorption capacity depends on a variety of factors such as aspects of hair morphology.     

Seasonal changes in the concentrations of nitrogen and phosphorus in farmland drainage and groundwater of the Taihu Lake region of China

Monte Carlo simulations were performed using the GEANT4 code for the investigation of γ-ray absorption in water in different spherical geometries and of the efficiency of a NaI(Tl) detector for different radionuclides in the aquatic environment. In order to test the reliability of these simulations, experimental values of the NaI(Tl) detector efficiency were deduced and seem to be in good agreement with the simulated ones. In addition, using the simulated efficiency, an algorithm was developed to determine the minimum detectable activity in becquerels per cubic meter in situ as a function of energy for typical freshwater and seawater spectra.     

Effects of sampling techniques on physical parameters and concentrations of selected persistent organic pollutants in suspended matter

This study focusses on the effect of sampling techniques for suspended matter in stream water on subsequent particle-size distribution and concentrations of total organic carbon and selected persistent organic pollutants. The key questions are whether differences between the sampling techniques are due to the separation principle of the devices or due to the difference between time-proportional versus integral sampling. Several multivariate homogeneity tests were conducted on an extensive set of field-data that covers the period from 2002 to 2007, when up to three different sampling techniques were deployed in parallel at four monitoring stations of the River Rhine. The results indicate homogeneity for polychlorinated biphenyls, but significant effects due to the sampling techniques on particle-size, organic carbon and hexachlorobenzene. The effects can be amplified depending on the site characteristics of the monitoring stations.     

Statistical analysis of PM10 concentrations at different locations in Malaysia

Malaysia has experienced several haze events since the 1980s as a consequence of the transboundary movement of air pollutants emitted from forest fires and open burning activities. Hazy episodes can result from local activities and be categorized as "localized haze". General probability distributions (i.e., gamma and log-normal) were chosen to analyze the PM(10) concentrations data at two different types of locations in Malaysia: industrial (Johor Bahru and Nilai) and residential (Kota Kinabalu and Kuantan). These areas were chosen based on their frequently high PM(10) concentration readings. The best models representing the areas were chosen based on their performance indicator values. The best distributions provided the probability of exceedances and the return period between the actual and predicted concentrations based on the threshold limit given by the Malaysian Ambient Air Quality Guidelines (24-h average of 150 μg/m(3)) for PM(10) concentrations. The short-term prediction for PM(10) exceedances in 14 days was obtained using the autoregressive model.