Occurrence of Organotin Compounds in the Aquatic Environment of Greece

The presence of organotin (OT) compounds was investigated in coastal areas (10 stations), wastewater treatment systems (six stations), rivers (19 stations) and lakes (12 stations) throughout Greece, in three sampling campaigns organized between October 1998 and September 1999. A screening method for the determination of toluene extractable organotins (TEOTs) by Electrothermal Atomic Absorption Spectrometry (ETAAS) was used during the first two sampling campaigns. TEOTs (sum of tributyltin, TBT, dibutyltin, DBT and triphenyltin, TPhT) were detected in most seawater and wastewater samples at concentrations up to 19.4 and 89.9 ng l^?1, respectively, while they were detected occasionally in surface water. During the third sampling campaign, OT compounds were extracted in selected stations using direct derivatization with NaBEt₄ in acidic medium and analysed by Gas Chromatography–Mass Spectrometry (GC–MS). In seawater, the levels of TBT, DBT and monobutyltin (MBT) were varied between < 2 and 70, 159 and 19 ng l^?1, respectively and tend to decrease with increasing distance from the coastline. TPhT was not detected in any of the samples. Significant concentrations of OT species were detected in influent wastewater, up to 384, 76.2 and 67.8 ng l^?1 for TBT, DBT and MBT, respectively. OTs were mainly associated with the suspended solids and were totally removed during wastewater treatment.     

Organotin Compounds in Sediments from the Göta älv Estuary

Concentrations of organotin compounds in sediments from four sites in the Göta älv estuary, SW Sweden, rangefrom 17 to 366 ng/g dw for tributyltin (TBT) and from1.5 to 71 ng/g dw for triphenyltin (TPT), similar toresults from other harbours and marinas and from an earlier study in the Göteborg Harbour, which is located in the estuary. Also dibutyltin, monobutyltin, diphenyltin and monophenyltin, the degradation products of TBT and TPT, werefound. TBT concentrations are the highest in the inner harbour and in the upper sediment layer of ca. 10 cm, indicating the risk for mobilisation of TBT bound in surface sediments in thefrequently disturbed harbour environment.     

A Survey of Organotin Compounds in the Northern Adriatic Sea

The extent of pollution with organotin compounds was investigated in water, sediment and bivalve mussels (Mytilus galloprovincialis) from the Northern Adriatic Sea. Butyl-, phenyl- and octyltin species were quantified after extraction and derivatisation by gas chromatography–mass spectrometry in a total of 99 samples from the period from 2000 to 2006. The accuracies of the analytical procedures were checked by spiking of unpolluted water samples and by the analysis of standard reference materials (harbour sediment PACS-2 and mussel tissue ERM-CE 477). Among organotin species analysed in samples butyltins were the predominant. Tributyltin was found to be present in the highest concentrations, suggesting its recent input into the marine environment. Butyltins were detected at all sites surveyed (sum of butyltins was up to 718 ng Sn L^?1, 3,552 ng Sn g^?1 d.w. and 9,991 ng Sn g^?1 d.w. in water, sediment and mussel samples, respectively), phenytins in much lower concentrations (up to 31 ng Sn L^?1, 326 ng Sn g^?1 d.w. and 442 ng Sn g^?1 d.w. in water, sediment and mussel samples) and to a much smaller extent, while octyltins were not detected at any location. The spatial distribution of tributyltin was closely related to boating, with the highest concentrations found in marinas (up to 586 ng Sn L^?1 for water samples, 1,995 ng Sn g^?1 d.w. for sediment and 6,434 ng Sn g^?1 d.w. for mussel samples). The temporal distribution clearly indicates a decrease of organotin pollution at all sites.     

Distribution and Fate of Organotin Compounds in Japanese Coastal Waters

In order to elucidate the details of both the distribution and fate of organotin compounds (OTs) in the costal ecosystem, the concentrations of butyltin compounds (BTs) and phenyltin compounds (PTs) were determined in seawater, sediment and blue mussels Mytilus galloprovincialis collected in Maizuru Bay, Japan. The concentrations of tributyltin (TBT) in seawater, sediments and mussels ranged from 3.9 to 27 ng l^?1, from 1.2 to 19 ng g^?1 dry wt and from 0.77 to 11 ng g^?1 wet wt, respectively. Although the levels of TBT in seawater, sediments and mussels from Maizuru Bay were lower than those reported previously at other sites in Japan, the levels can still be toxic to susceptible organisms. Trace amounts of PTs were also found in seawater, sediment and mussel samples, indicating that there is a slight input of triphenyltin (TPT) into the seawater in the bay at present. The highest TBT concentration in seawater among all sites measured in the bay was found near a glass factory, and the lowest concentrations were observed at the center of the bay. The highest concentration of TBT in sediment was detected near a shipyard. In mussels, a high concentration of TBT was detected near a cement plant and timberyard. These results indicate that the major sources of contamination of OTs in the bay are considered to be from those facilities and ships. The proportion of TBT in seawater and mussels showed that, of total BTs, it was the predominant compound at most sites. These results suggested that there is a continuous input of TBT into the seawater and thereafter an accumulation of TBT in mussels due to their low metabolic capacity to degrade TBT. In sediment, the proportion of monobutyltin (MBT) was the highest of BTs at most sites. This could reflect a previous contamination by TBT used before the regulation of its usage in the bay.     

Antimony as a Tracer of the Anthropogenic Influence on Soils and Estuarine Sediments

The aim of this work was to evaluate antimony (Sb) as apotentially valuable tracer of the anthropogenic impact on soilsand estuarine sediments. Antimony was determined in fifteenroadsoils from a medium-size city, La Coruña (NW of Spain);and twelve sediments from two estuaries (La Coruña and Ares-Betanzos). Sb determination was accomplished in a rapid andreliable way by directly measuring the solid samples with anautomatic ultrasonic slurry sampling-ETAAS device. Soil contentsranged from 0.29 to 8.81 μg g^-1. A relation between Sbconcentration and motor vehicle intensity was observed.Regarding estuarine sediments, Sb amounted from 0.22 to 1.51 μg g^-1, for the La Coruña estuary and 0.24 to 0.71 μg g^-1, forthe Ares-Betanzos estuary; higher Sb values were found forcoastal locations whereas lower contents corresponded to `inner'samples. In order to confirm these findings, other pollutantswere studied: As, Cd, Co, Cr, Cu, Ni, Pb, Zn, aliphatichydrocarbons (AH) and polycyclic aromatic hydrocarbons (PAH).These values, along with the Sb ones, were subjected tomultivariate studies intended to elucidate whether Sb correlated(and to what extent) to other well-known anthropogenic pollutants. Thus, Sb became associated to Cd, Cu, Pb and Zn in road soils and to As, Cu, Zn, PAH, Pb and unresolved hydrocarbons, in sediments.     

The Effect of Former Mining Activities on Contamination Dynamics in Sediments,Surface Water and Vegetation in El Avenque Stream,SE Spain

This work aims to identify and characterize heavy metal contamination in a fluvial system from Cartagena–La Unión mining district (SE Spain). In order to assess the dynamics of transport and the accumulation of heavy metals, sediments, surface water and vegetation, samples along “El Avenque” stream were collected. The former direct dumps of wastes and the presence of tailing ponds adjacent to the watercourse have contributed to the total contamination of the stream. Total Cd (103 mg kg⁻¹), Cu (259 mg kg⁻¹), Pb (26,786 mg kg⁻¹) and Zn (9,312 mg kg⁻¹) in sediments were above the limits of European legislation, being highest where tailing ponds are located. Bioavailable metals were high (3.55 mg Cd kg⁻¹, 6.45 mg Cu kg⁻¹, 4,200 mg Pb kg⁻¹ and 343 mg Zn kg⁻¹) and followed the same trend than total contents. Metals in water were higher in sampling points close to ponds, exceeding World Health Organization guidelines for water quality. There is a direct effect of solubilisation of sediment metals in water with high contents of SO₄²⁻, product of the oxidation of original sulphides. The mobility of metals varied significantly with shifts in pH. Downstream, available and soluble metals concentrations decreased mainly due to precipitation by increments in pH. As a general pattern, no metal was bioaccumulated by any tested plant. Thus, native vegetation has adopted physiological mechanisms not to accumulate metals. This information allows the understanding of the effect of mining activities on stream contamination, enforcing the immediate intervention to reduce risks related to metals’ mobility.     

Occurrence of Guanidino Compounds in Several Plants

The stored nitrogen in perennial plants plays an important role in their regrowth in spring. Free L-arginine is one of the major forms of stored nitrogen (6, 9) .. LArginine is metabolized via the urea cycle in animal and plant tissues. In animal tissues, L-arginine is also metabolized via r-guanidinobutyramide, r-guanidinobutyric acid, and r-aminobutyric acid to the TCA cycle. In plant tissues, few attempts have been made to study arginine-metabolic routes other than the urea cycle. In white spruce tissues (3), L-arginine is metabolized via r-guanidinobutyric acid. Also in citrus tissues (4, 5), the operation of the same metabolic route has been reported. In these experiments, it was observed that various guanidino compounds reacted with the Sakaguchi reagent.

To obtain more information about the guanidino compounds involved in the arginine metabolism, the analytical system was evaluated and the presence of these compounds in several plant species was examined.     

Occurrence of Pesticides in Water, Sediments, and Fish Tissues in a Lake Surrounded by Agricultural Lands: Concerning Risks to Humans and Ecological Receptors

Lake Vela (Littoral Centre of Portugal) is considered a natural habitat with community interest and consequently was included in the Natura 2000 Network. However, this freshwater ecosystem has been potentially exposed to diffuse pollution generated by agricultural and livestock activities, which seriously compromise its ecological balance. As part of the Ecological Risk Assessment (ERA) proposed for Lake Vela, this study aimed to evaluate the occurrence of pesticides in different compartments: surface water, groundwater, sediments, and fish tissues. Moreover, to assess potential concerning effects on ecosystem and human health, the measured concentrations of pesticides were compared with regulatory and toxicological benchmarks. The results confirmed the presence of high concentrations of pesticides, including organochloride pesticides banned decades ago, in surface water, groundwater, and sediment. The measured concentrations of pesticides, compared with toxicological benchmarks, indicated that harmful effects are likely for aquatic species due to the presence of alachlor, aldrin, and dieldrin. Additionally, the concentrations of pesticides detected in groundwater were also above the recommended safety levels for drinking water, which constitutes a concern for the local population’s health. Results also showed an accumulation of alachlor in predator and benthic fish species which could represent a risk to human consumers and particularly to the regular fish predators (e.g., otters and birds). This study, as the first exposure characterization performed on the Lake Vela system, constitutes valuable and useful information for the ERA process. Although this preliminary assessment of risks should be continued and confirmed through a weight-of-evidence approach, it had already unraveled how concerning are the problems in this ecosystem and the urgency of implementing restoration measures to guaranty its sustainability. Furthermore, this study reinforces the importance of evaluating similar freshwater ecosystems that are also highly threatened by diffuse pollution.     

Occurrence of Sexual Hormones in Sediments of Mangrove in Brazil

The presence of sexual hormones (female estrogens) was assessed in sediments of a mangrove located in the urban region of southern Brazil. The estrogens are involved in human sexual reproduction. They act as the chemical messengers, and they are classified as natural and synthetic. The estrogens inputs in the environment are from treated and untreated sewage. The presence of estrogens in sewage is excretion from the female due to natural production and use of contraceptives (synthetic estrogens). With the indiscriminate release of sewage into the environment, estrogens can be found in rivers, lakes, and even in oceans. In this work, the presence of estrone (E1), 17-??-estradiol (E2), and 17-??-ethynilestradiol (EE2) in eight sedimentary stations in Itacorubi mangrove located on Santa Catarina Island, south Brazil, was investigated. Historically, the Itacorubi mangrove has been impacted by anthropogenic activities because the mangrove is inserted in the urban area of the Florianopolis. The estrogen EE2, used as contraceptive, had the highest concentration in mangrove sediment, 129.75?±?3.89 ng/g. E2 was also found, with its concentration ranging from 0.90?±?0.03 to 39.77?±?1.19 ng/g. Following the mechanism, under aerobic or anaerobic conditions, E2 will first be oxidized to E1, which is further oxidized to unknown metabolites and finally to CO₂ and water (mineralized). EE2 is oxidized to unknown metabolites and also finally mineralized. Theoretically, under anaerobic conditions, EE2 can be reduced to E1 even in environments such as mangrove which is essentially anaerobic.     

Surface Water Quality Impacts of Conservation Tillage Practices on Burley Tobacco Production Systems in Southwest Virginia

A plot-scale, rainfall-simulation study measured edge-of-field pollutant losses from conventional-till, strip-till, and no-till treatments in a burley tobacco production system. The field experiment results show that the conventional-till treatment yielded more total runoff than strip- and no-till treatments. Compared to the conventional-till treatment, both no-till and strip-till reduced the total mass losses of total suspended solids (TSS), total nitrogen (TN), total Kjeldahl nitrogen (TKN), nitrate (NO-N), ammonia (NH₃-N), total phosphorus (TP), orthophosphate (PO₄-P), and the insecticide chlorpyrifos in runoff. Although statistical analyses indicated that there was no significant difference between the no-till and strip-till practices, the no-till practice consistently yielded less edge-of-field pollutant loss than the strip-till practice. This research reinforces the body of knowledge documenting the effectiveness of conservation-tillage practices in reducing edge-of-field pollutant losses.     

Assessment of Metals in Sediments in a Tributary of Guadalquiver River (Spain). Heavy Metal Partitioning and Relation between the Water and Sediment System

A physical-chemical characterisation of the sedimentsof the Guadaira River in Southwest Spain has beencarried out, determining twenty-three parameters persample. Non-treated urban sewage and industrialwastewaters from olive oil and table olives affectthis river. The factor analysis of the data showshigh organic matter contents with metallicpollution. Consequently, points downstreamstand out because of very high organic and metallicpollution (Zn, Pb, Cr, Cu and Cd, in order ofabundance, showing concentrations in sediments rangingfrom 50–7500 times those of waters). Heavy metals partitioning studies can be a goodapproach to show the real activity of these metals in theaquatic environment. We applied Tessier's analytical sequential extraction scheme to sediments.Sediments would be in general mildly hazardous because wefound low levels of easily interchangeable metals in the first fraction. Nevertheless, that is not thecase in the river's last stretch, precisely wheresediments are most abundant, the heavy metal levelslargest and dredgings are made periodically. Here,their disposal is of concern; since the actual use ofthese sediments as organic amendment for agriculturalsoils is unacceptable.Interaction between waters and sediments in theriverbed by means of correlation, factor and clusteranalysis on waters and sediments data, wasinvestigated. With this approach we concluded that inthe final stretch there is a problem of contaminationof both, sediments and waters. However, in the middlecourse only sediments are actually polluted. Thiscorresponds to the previous research, when thesituation of waters in this zone was even worse.     

Cadmium in the Water and Sediments of the Chao Phraya River and Associated Waterways, Bangkok, Thailand

As part of a research programme designed to examine the effect of cadmium on various biochemical responses in fish, a preliminary survey was carried out of cadmium concentrations in water and sediments sampled at 26 sites within the Chao Phraya River system in the Bangkok area of Thailand. Compared with values in the literature, the results of total cadmium analysis of both river water and sediments gave no indication of extreme pollution with cadmium, although two sites were identified with substantially higher than average sediment cadmium concentrations. More detailed sampling at these sites, over several months, compared with nearby `pristine' sites, confirmed their elevated cadmium status. The forms of cadmium present in the sediments at these sites, as determined by sequential fractionation, also provided evidence for the presence of contamination. However, considerable temporal variations in water and sediment cadmium concentrations were observed at individual sites, most probably related to seasonal high water levels and sediment flushing.     

Fractionation and Distribution of Metals in Guadiamar River Sediments (SW Spain)

Traditionally, the Guadiamar River (Seville, Southwest Spain) has received pollution from two different sources, in its upper section, from a pyrite exploitation (Los Frailes mine) and, in its lower section, from untreated urban and industrial wastes and from intensive agricultural activities. In 1998, the accidental spillage of about 6 million m³ of acid water and sludge from mine tailings to Guadiamar River worsened the pollution of an already contaminated area. The main polluting agents of the spillage were heavy metals. The total concentration of a metal provides scarce information about the effects on environmental processes or about the toxicity of the sediment samples. A more sophisticated fractionation of the sediment samples based on a species distribution can help to understand the behaviour and fate of the metals. This article describes a distribution study of the metals Al, Cd, Cu, Fe, Mn, Pb and Zn by fractionation analysis of sediments from eleven sample sites alongside the Guadiamar Riverbed. The samples were collected in summer 2002, four years after the spillage and after the area had been cleaned. Sequential extraction analysis resulted in the definition of four fraction categories: exchangeable metal (the most available fraction), reducible metal (bound to hydrous oxides of Fe and Mn), oxidizable metal (bound to organic matter and sulphides) and a residual fraction (bound to minerals). Significant increases in the available fraction of several potentially toxic metal ions like Cd, Mn and Zn were found. The distribution pattern was variable along the River. At the site closest to the mineworks, the soluble forms of Cd, Mn and Zn were significantly more abundant that those downstream. Cu and Pb were present in the reducible fraction while Fe was present associated in the residual fraction.     

Speciation and Transformation of Sulfur in Freshwater Sediments: a Case Study in Southwest China

Sulfur (S) is one of the most redox-sensitive elements and has a marked impact on the geochemical cycling of biogenic elements in freshwater sediments. Current understanding of the speciation of sedimentary S, and of the processes regulating it, is insufficient. In this study, the speciation and spatial variations of S and iron (Fe) in sediments (soils) from Lake Hongfeng, one of the largest freshwater lakes in Southwest China, were investigated using X-ray absorption near-edge structure (XANES) spectroscopy and diffusive gradient in thin film technique (DGT). The results show that S in sediments and soils was composed of seven fractions in different electronic oxidation states (EOSs), including (i) reduced S (R-S, G1, EOS = ? 1), (ii) lowly oxidized S (LO-S, including G2-G5; EOS = 0, 0.5, 2, and 3.7), and (iii) highly oxidized S (HO-S, including G6 and G7; EOS = 5 and 6). Proportional differences of S speciation in sediments and soils indicated that HO-S is largely reduced to LO-S and R-S during depositional processes. The HO-S fraction decreased in the top surface sediments and then increased in the deeper layers, whereas the R-S fraction showed the opposite trend, suggesting that sulfate reduction and re-oxidation processes occurred in the sediments. High ratios of soluble Fe/S provided a favorable foundation for the reduction and burial of sedimentary S. The speciation and spatial variations of S in freshwater sediments are controlled by complex environmental factors, including terrigenous material discharges, water redox conditions, and porewater chemistry (such as for pH, Eh, and reactive Fe). Our study will help to deepen the understanding of the geochemical dynamics of S in the sediments of freshwater ecosystems.     

Measurement of Volatile Organic Compounds in Urban Air of La Coruña,Spain

Twenty-eight volatile organic compounds have been measured in a 3-month monitoring campaign. The sampling point is locatedin the urban centre of La Coruña, a medium-size town in theNorthwest of Spain. Only a petrol refinery can be consideredas an important point VOCs source in its surrounding area.The municipal landfill collapsed in September 1996, and rebuilding works caused strong odour episodes at the urbancentre. We tried to check how this problem affected urban airquality. Samples were taken with Tenax-TA tubes and analysedby thermal desorption-GC-MS. From the results obtained, traffic emissions were recognised as the main VOCs source inthe sampling zone. On November 9th a contaminationepisode took place. Aromatic and aliphatic compounds levelswere probably affected by emissions from fuel treatmentprocesses in a nearby petrol refinery. No influence onquantified VOCs concentrations from the remaking landfillworks was observed. Several compounds (organosulphurs, estersand alcohols) were recognised as the cause of odour problems.     

磷在富营养化湖泊沉积物-水界面的循环

沉积物中部分固定的磷可通过分解或溶解作用而释放磷酸盐到沉积物间隙水中;再生的磷可能释放到上覆水体中,或在沉积物中作为一种自生相而再沉淀,或被沉积物的其它组分所吸附。本文描述了磷在沉积物-水界面的迁移过程,并对影响磷循环的因子及其磷自沉积物释放的机制作一简要概述。     

Possibility of Reductive Deactivation of S-Triazines and Parent Compounds on Waters and Sediments

Electrochemistry can be a valuable instrument to preserve the aquatic environment, first, by elucidating the oxidation-reduction mechanisms of substances having toxicological potential at laboratory scale; second, by aiding through extrapolation to comprise the evolution and fate in the environment of these pollutants and, finally, by establishing the basis of some electrochemical deactivation processes at industrial scale. In this way, this paper deals on studies of a type of highly pollutant substances for the aquatic media such as the S-triazines. The first part of the paper is focused to show the electrochemical reduction behavior of some S-triazines (eleven compounds have been studied). Later, the probable consequences at natural scale of these electroreductive processes are evaluated. Thus, the electrochemical reduction of diluted solutions of s-triazine herbicides and parent compounds takes place at potentials of ?0.90 to ?1.20 V, at very acidic pH values. The electroreduction products generated in all cases have loss the aromaticity and, depending on the compound, the chlorine atom or the –SCH₃ group. So, the resulting molecules present lower toxicity than the original compounds. For this reason, the electroreductive way can be an efficient option for the detoxification of S-triazine polluted waters. On the other hand, the natural deactivation of the s-triazines present in natural waters, in addition to the conventional photooxidative route taking place in well illuminated and oxygenated waters, could take place through the reductive process when the waters are essentially anoxic, acidic, and rich in suspended materials. This natural reduction, moreover, could favour the later oxidation or metabolization of the byproducts emanating of the original plaguicides. Finally, the reduction of S-triazines, both forced (industrial water depuration via electrochemical reduction) and no forced (natural aquatic media) requires more negative redox potentials, that is, more reductive environments as the molecules become more complex.     

天津近郊地区淡水养殖水体的表层水及沉积物中典型抗生素的残留分析

利用固相萃取-高效液相色谱-串联质谱联用技术（SPE-HPLC-MS/MS）分析了天津近郊养殖水体的表层水及沉积物中喹诺酮类、四环素类及磺胺类3类共18种抗生素的残留,同时考察3类抗生素在不同季节的变化分布特征。结果表明,在淡水养殖水体的表层水中环丙沙星、恩诺沙星和土霉素等检出率较高,浓度范围在10.5～26.8μg·L-1之间;相对地,在养殖水体的沉积物中磺胺甲基异噁唑、磺胺甲噻二唑、磺胺二甲氧嘧啶、诺氟沙星的检出率较高,浓度范围在1.5～30.1μg·kg-1之间。研究同时发现,冬季3类抗生素在表层水和沉积物中的检出率和检出浓度普遍高于夏季。说明在我国部分淡水养殖地区的养殖水体中已经有一定量的磺胺类和喹诺酮类抗生素的残留,并可能威胁到水生生物的安全,进一步对人体健康产生危害,因此应加强对淡水养殖环境中抗生素残留的监测与管理。     

Mining Impacts on Trace Metal Content of Water,Soil, and Stream Sediments in the Hei River Basin,China

The impacts of mining to watersheds are highly variabledepending on the type of mining, processing of ores, andenvironmental factors. This study examined the Hei River incentral China, for impacts of gold and iron mining onconcentrations of metals in river water, river sediments andstream-channel soils. No production processing of ores occurson-site at either mine. Total metal content and extractablemetals using DTPA were determined. Total concentrations of Cd,Cu, Pb and Zn were high in some stream sediments and soils nearthe mine sites; metal concentrations ranged from 4–24, 11–100,11–380, and 33–1600 μg g^-1 for Cd, Cu, Pb, and Zn,respectively, in soil. Total cadmium was high in all soilsand sediments. Extractable metals were low, with the exceptionof Pb and Cu. At the gold mine, extractable Pb ranged from 8 to33%; extractable Cu ranged from 3 to 21% of total metalconcentration. Chromium and Ni were not above typicalconcentrations in either soils or river sediments. An abundance of carbonates, high river water pH, and high water flow rates all appear to contribute to limiting quantities of metals in the river water. If mining activities are not changed, impacts of mining on downstream metal concentrations in river water should be nominal.