FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al₂O₃) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L^?1 for H₂SO₄ concentration, system flow rate as 0.40 mL min^?1, sample injection volume of 192.50 μL, 2 min for preconcentration time, and 0.10 mol L^?1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 μM, linear correlation coefficient R?=?0.9997 and LOD?=?0.024 μM. The preconcentration factor of about four times was obtained through the passage of 800 μL of a standard solution containing 0.961 μM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 μL of NH₄OH 0.1 mol L^?1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 μL of HCl 0.02 mol L^?1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.     

丹江口库区坡耕地柑桔园不同覆盖方式下地表径流氮磷流失特征

以坡耕地柑桔园为研究对象,地表覆盖方式采用对照、秸秆覆盖和地膜覆盖3个处理,实验采用完全方案。结果表明,在本实验条件下,坡地地膜覆盖处理一定程度增加了径流量,而秸秆覆盖处理与对照每次降雨径流量基本相当;各处理土壤氮磷养分均有一定程度的流失,以氮素流失量较高,磷素流失量相对较低;在地膜覆盖条件下,柑桔园地表径流中N、P流失量较高,其总氮和总磷流失系数分别达0054%和0064%,而秸秆覆盖总氮和总磷流失系数最低;对不同地表覆盖方式柑桔园地表径流水体氮素形态特征分析表明,可溶性氮素占总氮的比例较高,可溶性氮素中又以NO-3 N为主,而NH+4 N所占的比重较低。以上结果说明,在丹江口库区,氮素污染风险要高于磷,防控的主要矛盾是氮,而秸秆覆盖是减少坡耕地养分流失较好的管理措施     

DNA and chromosomal damage induced in fish (Anguilla anguilla L.) by aminomethylphosphonic acid (AMPA)—the major environmental breakdown product of glyphosate

The assessment of the direct impact of breakdown products of pesticide components on aquatic wildlife is ecotoxicologically relevant, but frequently disregarded. In this context, the evaluation of the genotoxic hazard posed by aminomethylphosphonic acid (AMPA—the major natural degradation product of glyphosate) to fish emerges as a critical but unexplored issue. Hence, the main goal of the present research was to assess the AMPA genotoxic potential to fish following short-term exposures (1 and 3 days) to environmentally realistic concentrations (11.8 and 23.6 μg L^?1), using the comet and erythrocytic nuclear abnormalities (ENA) assays, as reflecting different levels of damage, i.e. DNA and chromosomal damage, respectively. Overall, the present findings pointed out the genotoxic hazard of AMPA to fish and, subsequently, the importance of including it in future studies concerning the risk assessment of glyphosate-based herbicides in the water systems.     

Frequency of micronuclei and of other nuclear abnormalities in erythrocytes of the grey mullet from the Mondego,Douro and Ave estuaries—Portugal

Fish are bioindicators of water pollution, and an increased rate of their erythrocyte nuclear morphological abnormalities (ENMAs)—and particularly of erythrocyte micronuclei (EMN)—is used as a genotoxicity biomarker. Despite the potential value of ENMAs and MN, there is scarce information about fish captured in Iberian estuaries. This is the case of the Portuguese estuaries of the Mondego, Douro and Ave, suffering from different levels of environmental stress and where chemical surveys have been disclosing significant amounts of certain pollutants. So, the aim of this study was to evaluate genotoxicants impacts and infer about the exposure at those ecosystems, using the grey mullet (Mugil cephalus) as bioindicator and considering the type and frequency of nuclear abnormalities of erythrocytes as proxies of genotoxicity. Sampling of mullets was done throughout the year in the important Mondego, Douro and Ave River estuaries (centre and north-western Portugal). The fish (total n?=?242) were caught in campaigns made in spring–summer and autumn–winter, using nets or fishing rods. The sampled mullets were comparable between locations in terms of the basic biometric parameters. Blood smears were stained with Diff-Quik to assess the frequencies of six types of ENMAs and MN (given per 1,000 erythrocytes). Some basic water physicochemical parameters were recorded to search for fluctuations matching the ENMAs. Overall, the most frequent nucleus abnormality was the polymorphic type, sequentially followed by the blebbed/lobed/notched, segmented, kidney shaped, vacuolated, MN and binucleated. The total average frequency of the ENMAs ranged from 73?‰ in the Mondego to 108?‰ in the Ave. The polymorphic type was typically ≥50 % of the total ENMAs, averaging about 51?‰, when considering all three estuaries. The most serious lesion—the MN—in fish from Mondego and Douro had a similar frequency (≈0.38?‰), which was significantly lower than that in the Ave (0.75?‰). No significant seasonal differences existed as to the MN rates and seasonal differences existed almost only in the Douro, with the higher values in AW. In general, the pattern of ENMAs frequencies was unrelated with the water physicochemical parameters. Considering the data for both the total ENMAs and for each specific abnormality, and bearing in mind that values of MN in fish erythrocytes >0.3?‰ usually reflect pollution by genotoxicants, it is suggested that mullets were likely being chronically exposed to such compounds, even in the allegedly less polluted ecosystem (Mondego). Moreover, data supported the following pollution exposure gradient: Mondego?<?Douro?<?Ave. The scenario and inferences nicely agree with the published data from chemical monitoring.     

Contamination levels of polychlorinated biphenyls in wild versus cultivated samples of female and male mussels (Mytilus sp.) from the Northwest Coast of Iberian Peninsula—new application for QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) methodology

A newly analytical method based on QuEChERS extraction followed by gas chromatography with mass spectrometry (GC-MS) analysis was developed and validated for the quantification of 18 PCBs in wild (from Matosinhos Beach, Portugal) and cultivated (from Ria de Arousa, Spain) mussel samples, pooled by sex. Wild animals showed higher PCB levels than cultivated mussels, with males from both origins, presenting an upper contamination profile comparing with females. This fact seems to be correlated with few biometric parameters, but other interdependencies, not addressed herein, such as distinct lipid contents between sexes, as a consequence of the gametogenic stage, may also explain this data. Overall, data reiterate the importance of investigating the presence of PCBs in marine biological samples, which can act both as bioindicators of environmental contamination, either as food quality controls for human health.     

红壤坡地水土保持植物措施下柑橘林地水文生态效应

根据江西水土保持生态科技园2001～2008年不同处理措施柑橘林地径流小区的降雨产流产沙的定位观测资料及2010年土壤含水量测试数据,分析了坡面尺度水土保持植物措施下柑橘林地的产流产沙及土壤水分的特征,研究了狗牙根带状覆盖、狗牙根全园覆盖、果园清耕3种措施下的蓄水保土效应。结果表明：有草被覆盖的柑橘林小区的产流产沙量明显小于柑橘清耕小区,狗牙根带状覆盖小区减流减沙效果最好,减流率为98.21%,减沙率为99.84%。在大部分土层深度,草被带状覆盖下的土壤水分含量最高,均大于清耕措施,而全园覆盖由于植物蒸腾耗水量大水分含量反而低于带状覆盖。条带植草是防治柑橘林地水土流失的有效措施,具有明显的减流减沙效应和蓄积水分作用     

Factors affecting 210Po and 210Pb activity concentrations in mussels and implications for environmental bio-monitoring programmes

The activity of ²¹⁰Po and ²¹⁰Pb was determined in mussels of the same size (3.5-4.0 cm shell length) sampled monthly over a 17-month period at the Atlantic coast of Portugal. Average radionuclide concentration values in mussels were 759 ± 277 Bq kg⁻¹ for ²¹⁰Po (range 460-1470 Bq kg⁻¹ dry weight), and 45 ± 19 Bq kg⁻¹ for ²¹⁰Pb (range 23-96 Bq kg⁻¹ dry weight). Environmental parameters and mussel biometric parameters were monitored during the same period. Although there was no seasonal variation of radionuclide concentrations in sea water during the study period, the concentration of radionuclide activity in mussels varied seasonally displaying peaks of high concentrations in winter and low concentrations in summer. Analysis of radionuclide data in relation to the physiological Condition Index of mussels revealed that ²¹⁰Po and ²¹⁰Pb activities in the mussel (average activity per individual) remained nearly constant during the investigation period, while mussel body weight fluctuated due to fat storage/expenditure in the soft tissues. Similar variation of radionuclide concentrations was observed in mussels transplanted from the sea coast into the Tejo Estuary. However, under estuarine environmental conditions and with higher food availability throughout the year, transplanted mussel Condition Index was higher than in coastal mussels and average radionuclide concentrations were 210 ± 75 Bq kg⁻¹ (dry weight) for ²¹⁰Po and 10 ± 4 Bq kg⁻¹ (dry weight) for ²¹⁰Pb, therefore lower than in coastal mussels with similar shell length. It is concluded that the apparent seasonal fluctuation and inter-site difference of radionuclide concentrations were mostly caused by mussel body weight fluctuation and not by radionuclide body burden fluctuation. This interpretation can be extended to the apparent seasonal fluctuation in concentrations of lipophilic and lipophobic contaminants in mussels, and provides an explanation for occasional high concentrations of ²¹⁰Po and man-made contaminants measured in mussels far from pollution sources.     

Immunosuppression in the infaunal bivalve Scrobicularia plana environmentally exposed to mercury and association with its accumulation

This study aimed to test the hypothesis whether mercury (Hg) activates or suppresses inappropriately the immunity of the bivalve Scrobicularia plana inhabiting a Hg contaminated area (Laranjo basin, Ria de Aveiro, Portugal). Immunity endpoints, as well as lipid peroxidation (LPO) as a sign of damage, were evaluated in parallel with total Hg burden. Bivalves from both moderately (MO) and highly (HI) contaminated sites displayed higher haemolymph Hg load and reduced plasma agglutination. Increased haemocytes density and decreased phagocytosis were observed at HI, whereas increased oxidative burst activity (OBA) was observed at MO, pointing out that the immunotoxicity is a result of Hg direct contact involving no ROS intervention. OBA observed at MO was concomitantly associated to peroxidative damage as depicted by LPO increase in haemocytes and haemolymph plasma. Thus, S. plana can be suggested as a suitable bioindicator of metal pollution in coastal areas on the basis of Hg bioaccumulation and immunotoxicity responses.     

Comparing the sensitivity of soil invertebrates to pesticides with that of Eisenia fetida

The sole routine testing of the standard earthworm Eisenia fetida for the terrestrial risk assessment of pesticides has been under much debate since other soil invertebrates may be more sensitive than this standard test species. However, the very low availability of laboratory toxicity data for taxa other than E. fetida has greatly hampered sensitivity comparisons. In the present study, the relative tolerance (T_rel) approach was used to enable comparing toxicity thresholds obtained from the US-EPA ECOTOX database, for main terrestrial taxonomic groups and pesticidal types of action (insecticides, fungicides, herbicides, and other) separately. Analyses confirmed previously reported lower and higher sensitivity of collembolans to fungicides and insecticides, respectively. However, various other discrepancies in susceptibility relative to E. fetida were encountered as indicated by species sensitivity distributions and/or calculated 95% confidence intervals of T_rel values. Arachnids and isopods were found to be more sensitive to insecticides, and nematodes to fungicides, as compared to E. fetida. Implications of study findings for the terrestrial risk assessment of pesticides are discussed.     

Percolation and batch leaching tests to assess release of inorganic pollutants from municipal solid waste incinerator residues

In this study, percolation and batch leaching tests were considered in order to characterize the behaviour of air pollution control (APC) residues produced in a municipal solid waste incinerator (MSWI) as a function of the liquid to solid ratio (L/S). This waste is hazardous, and taking into account their physical and chemical properties, leaching of contaminants into the environment is the main concern. In our work the leaching behaviour of toxic heavy metals (Pb, Zn, Cr, Ni and Cu) and inorganics associated with soluble salts (Na, K, Ca and Cl) was addressed. Although pH of the leaching solution is the most important variable, L/S may also play an important role in leaching processes. In our work, results from column and batch tests were compared in terms of concentration (mg/L) and releasing (mg/kg). The APC residues revealed to be hazardous according to both tests, and both Pb and Cl⁻ far exceeded the regulatory thresholds. The material exhibits high solubility, and when the liquid to solid ratio was high, more than 50% can be solubilised. The patterns of release may be in some cases availability or solubility controlled, and the former was easier to identify. When the results from column and batch experiments were compared by representing the cumulative released amounts (in mg/kg) as a function of L/S, both curves match for Zn, Ni, Cu, K, Na, Cl and Ca, but for Cr and Pb a significant difference was observed. In fact, the column experiments revealed that under percolation conditions it should be expected slow releasing of Pb along time. From this study, it can be concluded that the released amounts obtained in batch experiments for a certain L/S should be considered as the worst case for medium term. Some simple models proposed on the literature and based on local equilibrium assumption showed good fitting to experimental data for soluble species (non-reactive solutes).