Patrícia Palma

Sewage sludge, compost and other representative organic wastes as agricultural soil amendments: benefits versus limiting factors

Nine different samples of sewage sludges, composts and other representative organic wastes, with potential interest to be used as agricultural soil amendments, were characterized: municipal sewage sludge (SS1 and SS2), agro industrial sludge (AIS), municipal slaughterhouse sludge (MSS), mixed municipal solid waste compost (MMSWC), agricultural wastes compost (AWC), compost produced from agricultural wastes and sewage sludge (AWSSC), pig slurry digestate (PSD) and paper mill wastes (PMW). The characterization was made considering their: (i) physicochemical parameters, (ii) total and bioavailable heavy metals (Cd, Cr, Cu, Ni, Pb, Zn and Hg), (iii) organic contaminants, (iv) pathogenic microorganisms and (v) stability and phytotoxicity indicators. All the sludges, municipal or other, comply with the requirements of the legislation regarding the possibility of their application to agricultural soil (with the exception of SS2, due to its pathogenic microorganisms content), with a content of organic matter and nutrients that make them interesting to be applied to soil. The composts presented, in general, some constraints regarding their application to soil, and their impairment was due to the existence of heavy metal concentrations exceeding the proposed limit of the draft European legislation. As a consequence, with the exception of AWSSC, most compost samples were not able to meet these quality criteria, which are more conservative for compost than for sewage sludge. From the results, the composting of sewage sludge is recommended as a way to turn a less stabilized waste into a material that is no longer classified as a waste and, judging by the results of this work, with lower heavy metal content than the other composted materials, and without sanitation problems.

Risk assessment of representative and priority pesticides, in surface water of the Alqueva reservoir (South of Portugal) using on-line solid phase extraction-liquid chromatography-tandem mass spectrometry.

Surface waters located in intensive agricultural areas are more vulnerable to the pesticides contamination, which is a major concern if the water is intended to be used for human consumption. The aim of this study was to evaluate the presence and the distribution of pesticides in the Alqueva reservoir, an important source of water supply (South of Portugal), considering their representativeness in the agricultural practice of the area. For the analysis of pesticides risk impact we used the environmental quality standards in the field of water policy proposed recently by the European Commission. The pesticides belonging to the classes of phenylureas, triazines, chloroacetanilides, organophosphorous and thiocarbamates were analysed by on-line solid phase extraction-liquid chromatography-tandem mass spectrometry. The pesticides more frequently detected were atrazine, simazine, diuron and terbuthylazine. The highest levels of these pesticides were registered in spring, after pesticides treatment, namely in olive-tree and vine crops. The priority pesticides atrazine and diuron reached values above the annual average proposed in the European Union Legislation. The herbicide atrazine reached values that surpassed the proposed maximum allowable concentration (2,000 ng L(-1)). The sampling stations most affected by these pesticides were Sra. Ajuda, Lucefecit and Alcarrache, located in the northern part of the reservoir, closer to Spain where the agricultural activity is more intensive.

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.

Evaluation of surface water quality using an ecotoxicological approach: a case study of the Alqueva Reservoir (Portugal)

Background, aim, and scopeFreshwater reservoirs can be impacted by several hazardous substances through inputs from agricultural activity, sewage discharges, and groundwater leaching and runoff. The water quality assessment is very important for implementation of the monitoring and remediation programs to minimize the risk promoted by hazardous substances in aquatic ecosystems. Evaluation of the degree of contamination of aquatic environments must not take in account only its chemical characterization but it must be complemented with biological assays, which determine potential toxic effects and allows an integrated evaluation of its effects in populations and aquatic ecosystem communities. The application of this type of strategy has clear advantages allowing a general evaluation of the effects from all the water components, including those due to unknown substances and synergic, antagonistic, or additive effects. There are only a few studies that reported ecotoxicological acute end points, for the assessment of surface water quality, and the relationship among toxicity results and the anthropogenic pollution sources and the seasonal period. The aim of this study was to assess the ecotoxicological characterization of the surface water from Alqueva reservoir (South of Portugal) and to evaluate the influence of anthropogenic sources of pollution and their seasonal variation in its toxicity. The construction of Alqueva reservoir was recently finished (2002) and, to our knowledge, an ecotoxicological assessment of its surface water has not been performed. Because of that, no information is available on the possible impact of pollutants on the biota. The surface water toxicity was assessed using acute and chronic bioassays. The results are to be used for developing a monitoring program, including biological methods.Materials and methodsWater samples were collected during 2006–2007, at each of the nine sampling sites selected in Alqueva reservoir. These sampling points allow an assessment at the upstream (Sra. Ajuda, Alcarrache, Álamos-Captação), at the middle (Alqueva-Montante, Alqueva-Mourão, Lucefecit), and at the downstream of the water line (Alqueva-Jusante; Ardila-confluência; Moinho das Barcas). The campaigns occurred in February, March, May, July, September, and November of 2006 and February, March, and May of 2007. The rainy season comprised November, February, and March, and the dry season included May, July, and September. A total of 81 samples were collected during the study period. The physical–chemical parameters were analyzed following standard and recommended methods of analysis (APHA et al. 1998). The pesticide analyses were performed using gas chromatography according to DIN EN ISO 6468 (1996). Surface water ecotoxicity was evaluated using the following bioassays: Vibrio fischeri luminescence inhibition, Thamnocephalus platyurus mortality, and Daphnia magna immobilization and reproduction assay. The Spearman rank correlation coefficients were used to evaluate the associations between the water sample physicochemical properties (from each sampling station in each season) and the acute and chronic toxicological effects, with a level of significance p < 0.05.ResultsIn the acute toxicity study, the species that was found to be the most sensitive was T. platyurus. T. platyurus detected a higher number of toxic water samples during the dry season. Concerning the luminescent inhibition of V. fischeri, the results showed that this organism detected a great number of toxic water samples in rainy seasons. The water samples, which promoted higher toxic effects towards this species, were from the north and from the middle of the reservoir. The correlation analysis showed that V. fischeri luminescent inhibition (%) was positively correlated with total phosphorus, chlorpyrifos, iron, and arsenic. T. platyurus mortality (%) was positively correlated with the water pH, 5-day biochemical oxygen demand (BOD5), chlorides, atrazine, simazine, terbuthylazine, and endosulfan sulfate contents. Although the surface waters did not promote acute toxicity to the crustacean D. magna, in the chronic exposure, a significant decrease in the number of juveniles per female was observed, mainly at the dry period. The number of juveniles per female, in the reproduction test of D. magna, was negatively correlated with pH, temperature, BOD5, chloride, atrazine, simazine, terbuthylazine, and endosulfan sulfate. The water toxicity of the Alqueva water might be due principally to the intensive agriculture activities surrounding the reservoir and to the municipal wastewater discharges.DiscussionThe physicochemical parameters and the pesticide concentrations indicated that the water quality was worse in the north part of the reservoir system. These results are characteristic of the majority of reservoirs, once the construction of the dam promoted, by itself, the impounding of water flow and the increase of compound residence time. The toxicity tests corroborate with the chemical characterization. Acute toxicity of Alqueva water may be a result of the effect promoted by chlorpyrifos, endosulfan sulfate, phosphorus, and iron. Chronic toxicity may be a result of the effect of herbicides, arsenic, organic matter, endosulfan sulfate in mixture. Hence, the water toxicity of the Alqueva might be due principally to the intensive agriculture activities surrounding the reservoir and to the municipal wastewater discharges.ConclusionsThis study has shown that a large number of samples from different sites of the Alqueva reservoir contained potentially toxic contaminants. The sites with impaired water quality were those located at the north of the reservoir and in the surrounding areas of intensive agricultural activity. The results demonstrated that the use of a screening of acute and chronic toxicity tests with organisms from different trophic levels and with distinct sensibilities allowed the detections of several patterns of toxicity from spatial and temporal variability promoted by natural or anthropogenic sources. The chronic responses showed, especially in the dry season, that some of the species belonging to this aquatic ecosystem might be at risk.Recommendations and perspectivesThe V. fischeri and T. platyurus are two species that should be used in the acute bioassays for the ecotoxicological monitoring programs of this reservoir. It is recommended that other species, such as a productive organism (algae), be included in the next study, once the water reservoir had high levels of herbicides. Ecotoxicological assessment of surface water must integrate initial screening based on acute tests followed always by chronic bioassays. The results implicitly suggest that the implementation of processes of remediation by reducing pollutant input into the reservoir and by the implementation of water treatment processes is important and necessary.

A contribution towards the risk assessment of soils from the São Domingos Mine (Portugal): Chemical, microbial and ecotoxicological indicators

This study is a contribution towards a risk assessment of the São Domingos Mine area (Portugal), integrating information from: soil physicochemical characteristics, pseudo-total and bioavailable trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn), ecotoxicological evaluation, and microbial indicators. The bioassays using soil eluates (seed germination, luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) confirmed the soil toxicity categorization obtained with the bioassays using soil (plant growth tests, Eisenia fetida mortality and avoidance behaviour). However, the soil identified as the most toxic using bioassays, was different from the expected when considering the results from pseudo-total and effective bioavailable trace elements. Taking in consideration the observations, it is highly recommended to complement the results from environmental chemistry with results from bioassays, in order to provide a more complete and relevant information on the bioavailability of contaminants and to characterize the risk of contaminated soils.

Effects of atrazine and endosulfan sulphate on the ecdysteroid system of Daphnia magna.

The ecdysteroid system is used by crustaceans and other arthropods as the major endocrine signalling molecules, regulating processes such as molting and embryonic development. The aim of this study was to evaluate the ecdysteroid activity of two pesticides (atrazine and endosulfan sulphate), with distinct modes of action and which act in the juvenoid system of the crustacean Daphnia magna as weak juvenoid compounds. To assess the ecdysteroid activity, we first exposed maternal daphnids and embryos to nominal concentrations of the pesticides and determined the effect promoted by these pesticides on the molting frequency and on abnormalities in the embryos development. Furthermore, we evaluated if the toxic effects observed with the isolated pesticides were promoted or not by the disruption of the ecdysteroids system of the crustacean, by co-administrating of them with 20-hydroxyecdysone hormone. This hormone is the prime form of the invertebrates ecdysteroids system and it is responsible for the crustacean molting process. Both pesticides induced an increase of embryo abnormalities development. Endosulfan sulphate promoted a delay in the molting process. The effects induced by atrazine were not altered by co-exposure to 20-hydroxyecdysone. In contrast, the co-administration of 20-hydroxyecdysone allowed the reversion of the effects on both the molting process and embryonic development elicited by endosulfan sulphate. These results suggest that atrazine promotes its toxicity without interfering with the ecdysteroid activity of the crustacean. On the contrary, endosulfan sulphate is an anti-ecdysteroidal compound for D. magna.

Embryo-toxic effects of environmental concentrations of chlorpyrifos on the crustacean Daphnia magna

Chlorpyrifos is a non-systemic organophosphorus insecticide leading to the inhibition of the enzyme cholinesterase. Nowadays, this insecticide is widely used on a variety of crops and is frequently detected in surface waters around the world. The main aims of this study were to evaluate the effects of this insecticide on the embryonic development of Daphnia magna, and to assess the sensitivity of this endpoint in comparison with the endpoint of the chronic 21-day test. The featured endpoints were the number of offspring per female and abnormalities of both offspring and embryos. Chlorpyrifos exhibited significant toxic effects on the embryonic development manifested in the appearance of abnormalities, including arrested eggs, in 20% of the embryos exposed to a concentration of 0.01 microgL(-1). Furthermore, chronic exposition to the insecticide yielded a proportion of offspring abnormalities in later stages of development of about 43% at 0.01 microgL(-1). In contrast, a significant reduction in the number of offspring produced per female was only observed above a concentration of 0.03 microgL(-1). Hence, these results suggest that developmental abnormality was a more sensitive endpoint than the number of offspring production per female.

Endosulfan sulphate interferes with reproduction, embryonic development and sex differentiation in Daphnia magna

Endosulfan sulphate is the transformation product of endosulfan and it is the most frequent form of surface water contamination with endosulfan. The aim of this study was to evaluate the possible effects promoted by endosulfan sulphate in changes on the life cycle, embryo development and sex differentiation of Daphnia magna. The endpoints used were moulting frequency, fecundity, growth, developmentally abnormalities and sexual differentiation. The nominal concentrations of endosulfan sulphate tested ranged from 9.2 to 458.7 microg L(-1). Endosulfan sulphate promoted a significant decrease of the offspring number in all concentrations. Results showed a reduction of the size of females, together with a decrease in moulting frequency. Furthermore, an increase in embryo deformities was observed at all concentrations tested. Above a concentration of 91.7 microg L(-1) there was an increased production of males. The results suggest that endosulfan sulphate interferes with the life cycle and sex determination of the crustacean D. magna.

Assessment of the pesticides atrazine, endosulfan sulphate and chlorpyrifos for juvenoid-related endocrine activity using Daphnia magna.

The water flea Daphnia magna belongs to the cyclical parthenogenic species, which can reproduce by either parthenogenesis or sexual reproduction. Recent studies have reported the involvement of the methylfarnesoate hormone, in male sex determination of D. magna. The aim of this study was to evaluate the juvenoid and anti-juvenoid activity of atrazine, endosulfan sulphate, and chlorpyrifos. To assess the juvenoid activity we exposed maternal daphnids to several concentrations of the respective pesticides, using the percentage of male production as endpoint. Fenoxycarb (1microgL(-1)) was used as a positive control. The anti-juvenoid activity was assessed using a similar bioassay after the addition of fenoxycarb (1microgL(-1)) to all test solutions. Fenoxycarb is an insect growth regulator that mimics the action of methylfarnesoate, and promoted the production of 95% of male offspring at the given concentration. Weak juvenoid-agonist activity was detected for endosulfan sulphate, with a significant increase of the percentage of male daphnids detected through logistic regression. In addition, atrazine and endosulfan sulphate antagonized the juvenoid activity of fenoxycarb. These results also corroborate the hypothesis that weak juvenoid agonists can simultaneously act as juvenoid antagonists as it has been observed in other hormonal systems.

Spatial and temporal variability of the water and sediments quality in the Alqueva reservoir (Guadiana Basin; southern Portugal).

The purpose of this work was to evaluate the dynamic of the water quality from the Alqueva reservoir (Guadiana River Basin, Portugal) and identify the most important parameters that influence its ecological and chemical status. The results could indicate preventive and/or remediation actions that are necessary to improve its quality and status. Water and sediment samples were collected between 2011 and 2012, at five sampling stations, and analyzed for: (i) water - pH, temperature, dissolved oxygen, electrical conductivity, chloride, total phosphorus, total nitrogen, ammonium, nitrate, nitrite, biochemical and chemical oxygen demand, total Fe, Mn, and As; and (ii) sediments - pH, electrical conductivity, organic matter, total nitrogen, total phosphorus, major and trace elements. The results from the water column showed that the organic descriptors exceeded the Portuguese guideline values for water quality for multiple uses at most of the sampling stations. As for nutrients, Ajuda is the station where the concentrations of the total nitrogen and total phosphorus exceeded the guideline values in most months. Ammonium achieved concentrations above the allowed, during the study, in all locations. Trace elements were more abundant in the sediments, surpassing the maximum levels for the protection of aquatic life for As, Cd and Pb, at Alcarrache, Lucefécit and Álamos, respectively. The use of multivariate analysis showed that the major parameters that explained the water quality variability were the nutrients in the water column, and trace elements in the sediments. Comparing the results from this study with results obtained since 2006, we can observe an obvious increment of the organic descriptors and nutrients in the water body. Further, several parameters and observations indicate an increase of the eutrophication process. So, it is urgent to develop preventive actions and remediation processes to stop the degradation so as to improve the quality of the water in this reservoir.