Simultaneous Determination of O- and P- Nitrophenol by First Derivative Spectrophotometry

A simple method by first derivative spectrophotometry is proposed for the simultaneous determination of o-nitrophenol and p-nitrophenol. The analytes were separated from samples by liquid-liquid extraction (pH = 7.4) as tetrabutylammonium ion pairs into the 1,2-dichloroethane organic phase and subsequently the extracts were evaluated directly by derivative spectrophotometry. Simultaneous determination of both analytes could be carried out using the zero-crossing and the graphical methods for o-nitrophenol and p-nitrophenol, respectively. The determination ranges were found to be between 0.115 to 3.00 ppm and 0.130 to 3.00 ppm for o-nitrophenol and p-nitrophenol, respectively. The relative standard deviations were in all instances less than 2.0%. The proposed method was applied to the determination of these compounds in fruit juices.     

Sources, transport and reactivity of anionic and non-ionic surfactants in several aquatic ecosystems in SW Spain: a comparative study

Presence, distribution and transport mechanisms of the four major synthetic surfactants -linear alkylbenzene sulfonates (LAS), alkyl ethoxysulfates (AES), nonylphenol ethoxylates (NPEOs) and alcohol ethoxylates (AEOs)- have been simultaneously studied in different aquatic ecosystems. Urban wastewater discharges and industrial activities were identified as the main sources for these compounds and their metabolites. LAS, AES and carboxylic metabolites remained in the dissolved form (87–99%). However, NPEOs and AEOs were mostly associated with particulate matter (65–86%), so their degradation in the water column was limited due to their lower bioavailability. It was also observed that sorption to the particulate phase was more intense for longer homologs/ethoxymers for all surfactants. With respect to surface sediments, AES levels were considerably below (<0.25 mg/kg) the values detected for LAS and NPEOs. Concentrations of AEOs, however, were occasionally higher (several tens of ppm) than those found for the rest of the target compounds in several sampling stations.     

Haematology, genotoxicity, enzymatic activity and histopathology as biomarkers of metal pollution in the shrew Crocidura russula

Haematological (WBC, RBC, Hgb and Hct) and genotoxicity (MNT) parameters, hepatic enzymatic activities (GST, GPx and GR), and a histopathological evaluation of liver, kidneys and gonads were assessed as general biomarkers of metal pollution in the shrew Crocidura russula inhabiting a pyrite mining area. Specimens exposed to metals presented a few significant alterations when compared with reference animals: GST activity decreased; micronuclei increased; and evident liver alterations related to metal exposure were observed. On the basis of all the parameters studied, age was an important factor that partly explained the observed variation, whereas sex was the least important factor. Significant correlations were also found between heavy metal concentrations and biomarkers evaluated, demonstrating the great influence of these metals in the metabolic alterations. To the best of our knowledge, these data constitute the first measurements of a battery of biomarkers in shrews from a mine site and are among the few available for insectivorous mammals.     

Application of manure and compost to contaminated soils and its effect on zinc accumulation by Solanum nigrum inoculated with arbuscular mycorrhizal fungi

Zn accumulation in Solanum nigrum grown in naturally contaminated soil in the presence of different types of organic amendments was assessed. Under the same conditions, the response of the plant to inoculation with two different isolates of arbuscular mycorrhizal fungi (AMF) (Glomus claroideum and Glomus intraradices) was also evaluated. S. nigrum grown in the non-amended soil always presented higher Zn accumulation in the tissues, with the addition of amendments inducing reductions of up to 80 and 40%, for manure and compost, respectively, and enhancing plant biomass yields. The establishment of S. nigrum in the Zn contaminated soil combined with the application of amendments led to a 70-80% reduction in the amount of Zn leached through the soil. The use of S. nigrum in combination with manure appeared as an effective method for reducing the effects of soil contamination, diminishing Zn transfer to other environmental compartments via percolation.     

Evaluation of stream ecological integrity using litter decomposition and benthic invertebrates

Biomonitoring programs to access the ecological integrity of freshwaters tend to rely exclusively on structural parameters. Here we evaluated stream ecological integrity using (a) benthic macroinvertebrate derived metrics and a biotic index as measures of structural integrity and (b) oak litter decomposition and associated fungal sporulation rates as measures of functional integrity. The study was done at four sites (S1, S2, S3 and S4) along a downstream increasing phosphorus and habitat degradation gradient in a small stream. The biotic index, invertebrate metrics, invertebrate and fungal communities' structure and sporulation rates discriminated upstream and downstream sites. Decomposition rates classified sites S4 and S2 as having a compromised ecosystem functioning. Although both functional and structural approaches gave the same results for the most impacted site (S4), they were complementary for moderately impacted sites (S2 and S3), and we therefore support the need for incorporating functional measures in evaluations of stream ecological integrity.     

Evaluation of various tests for the diagnosis of soil contamination by 2,4,5-trichlorophenol (2,4,5-TCP)

Soil response to contamination with 2,4,5-triclorophenol was studied to test the validity of the concept of Generic Reference Levels (GRL), the main criterion used to define soil contamination. Soil samples were artificially contaminated with doses between 0 and 5000 mg kg⁻¹ of 2,4,5-triclorophenol, and analysed by various tests. Where possible, the response of soils to the contaminant was modelled by a sigmoidal dose-response curve in order to estimate the ED₅₀ values. The tests provided different responses, but only microbial biomass-C and dehydrogenase and urease activities demonstrated soil deterioration in response to contamination. The results suggest that the diagnosis of soil contamination has been greatly simplified in the legislation by the provision of a single figure for each compound, and that the GRL concept could perhaps be substituted by measurement of ED₅₀ values, which better reflect the alteration of a soil due to the presence of a xenobiotic substance.     

Human health risks of petroleum-contaminated groundwater

BACKGROUND, AIM AND SCOPE: The volatile organic compounds Benzene, Toluene, Ethylbenzene and Xylene (BTEX) are commonly found in petroleum derivatives and, at relatively high levels, can be associated with human health risks. Due to industrial activities, accidental petroleum spills are the main route of soil and groundwater contamination. The aim of the present study was to evaluate the indoor health risks due to tap water consumption contaminated by BTEX. MATERIALS AND METHODS: BTEX indoor exposure can occur through three principal pathways: inhalation, ingestion and dermal absorption. A multiphase and multicomponent model was used to simulate BTEX transport in groundwater. For evaluation of human risks due to the use of contaminated tap water, a mathematical model was elaborated. RESULTS: BTEX concentrations in a drinking well were obtained as a function over time. These concentrations were used to obtain the exposure due to the use of water from the contaminated drinking well. In addition to showing the highest concentration in water, benzene was the compound that remained for a longer period before being completely degraded. For all the evaluated BTEX, oral ingestion was also the main pathway of exposure for adults, whereas the contribution of inhalation and oral exposition in children were seen to be of the same magnitude. The sensitivity analysis of BTEX total dose for adults showed that direct ingestion was the most significant factor, followed by shower time, volume of the shower room, inhalation rate, and shower flow rate. For children, the most significant variable was also direct ingestion, followed by shower time, volume of the shower room, and body weight. DISCUSSION: In the current design situation, there would not be any health risks by the use of BTEX-contaminated water to the general population living in the neighborhood of the petroleum spill. Therefore, no remediation measures in the area of the spill would be necessary. CONCLUSIONS: The present results indicate that the design of a good scenario can perform an accuracy risk assessment. This model can serve as a useful tool for predicting indoor exposure to substances for which no direct data are available, reducing monitoring efforts and observing how different processes affect outcomes. RECOMMENDATIONS AND PERSPECTIVES: These preliminary data allow the establishment of a basis for further investigations focusing on efficiently recovering petroleum from contaminated sites.     

Development of a harmonised phosphorus extraction procedure and certification of a sediment reference material

A harmonised procedure for the determination of the forms of phosphorus in freshwater sediments, developed in the frame of the European Programme, Standards, Measurements and Testing (SMT) has been used for a certification campaign for a reference material. This operationally defined scheme is a good compromise between method performance and reproducibility. Furthermore, the method is rather simple to implement and could be used by water managers on a routine basis. A homogeneous and stable sediment reference material has been prepared and will be available before mid 2001. The so-called SMT protocol, together with the reference material, are useful tools in the field of water management, especially at a time when quality assurance is of paramount importance in laboratory analyses. Knowledge of the bioavailable forms of phosphorus is important not only for analysis of sediments but also for sludge and soils. Therefore, the SMT protocol could be extended to these materials.     

In vivo effects of deltamethrin on some biochemical parameters of carp (Cyprinus carpio L.)

Thein vivo effects of deltamethrin (DM) on the blood sugar level, the acetylcholinesterase (AChE, EC 3.1.1.7) activities of the blood serum and various organs (heart, liver and intestine), the lactate dehydrogenase (LDH, EC 1.1.2.3), glutamic-oxaloacetic transaminase (GOT, EC 2.6.1.1), and glutamic-pyruvic transaminase (GPT, EC 2.6.1.2) activities of the blood serum, the adenosine triphosphatases (EC 3.6.1.3; Na⁺/K⁺-ATPase and Mg²⁺-ATPase) activities of the erythrocyte plasma membrane and the catalase (EC 1.11.1.6) activity of the liver were examined throughout 96 h in adult carp (Cyprinus carpio L.) Two sublethal concentrations, 1.0 and 1.5 µg/l of deltamethrin, were used. All fish survived the experiment except one, in an aquarium containing 1.5 ppb of DM, which died after 72 h.The AChE specific activity was significantly inhibited in the heart and intestine after 96 h at both concentrations compared to that in the control animals (P<0.05, Student'st-test), while there was no detectable difference between the two treatment. At the same time there was no detectable change in the liver. In the serum, the AChE activity almost remained unchanged; the only significant decrease could be measured after 96 h at 1.5 µg/l deltamethrin concentration. The blood glucose content exhibited interesting changes: after 24 h fish exposed at 1 µg/l DM seemed to be stressed, although this increase was not significant. When these fish became used to the new conditions (in practice this meant the presence of DM), the glucose level decreased, especially after 72 h. At the same time the control animals kept in similar circumstances showed a small insignificant decrease. Meanwhile fish in aquaria containing 1.5 µg/l DM reacted to the treatment with an increased blood glucose level after 48 h, and this did not change until the end of the treatment. The Na⁺/K⁺-ATPase activity decreased in a dose-dependant manner, while Mg²⁺-ATPase was less affected. A small increase in LDH level was observed, indicating damage of different muscle tissues. However, this phenomenon appeared only with the small dosage after 24 h (P<0.05). It has to be mentioned that the individual values varied to a large extent among of the eight fish.The GOT activities of the serum increased during the treatment. However, significant changes were only expressed after 72 and 96 h at 1 µg/l DM concentrations (P<0.01 andP<0.05), and after a similar long treatment at the high dosage (P<0.05, 72 and 96 h). The GPT did not change significantly in aquaria containing 1 µg/l DM. The only larger increase was measured after 96 h at 1.5 µg/l DM concentration (P<0.05). The catalase activity in the liver of treated carp remained practically at the same level compared to that in control fish.All these changes (concerning the primary effects of this compound) demonstrate the effect of DM on different fish enzymes, at low concentrations under laboratory conditions, which might be useful in practice for biomonitoring using fish.