Chemical,biological, and ecotoxicological assessment of pesticides and persistent organic pollutants in the Bahlui River,Romania

Background, aim, and scope

Current knowledge on environmental impacts of industrial activities in Romania, particularly persistent organic pollutants (POPs), indicates that environmental standards of the European Union are not systematically met. In our study area, additional sources of POPs are agriculture and domestic wastes. Very scarce information is available upon environmental contaminations and effects. In the present study, we investigated the chemical pollution and their eventual impact on the ecosystem by measuring POPs and by using biological indicators of pollution.

Materials and methods

The survey was carried out at six main sample sites along the Bahlui River. Sediments were chemically analysed for their content in polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs)—hexachlorocyclohexanes (HCHs) isomers and the dichlorodiphenyl trichloroethane (DDT) family. River water was biologically monitored at the level of phytoplankton and benthic invertebrates’ communities. Water samples from six locations have been analyzed for algal species composition and correspondence to various water quality indices. Biological samples have been taken from the same locations so as to calculate the macroinvertebrate indices. In the most polluted areas, as revealed by previous methods, toxicity was tested by exposing the green alga Pseudokirchneriella subcapitata and the cladoceran Daphnia magna to various dilutions of water sample.

Results

Important concentrations of POPs were identified only in sediments at river mouths (sites S5 and S6). Along the year, the sum of PCB concentrations ranged between 3 and 10 ng/g dw (S5), and between 4 and 26 ng/g dw (S6). Concentration of HCHs ranged between 0.4 and 3 ng/g dw (both S5 and S6) with a higher contribution of the gamma-HCH (30–70%), followed by beta-HCH (20–50%). The beta-HCH isomer was found at lower concentrations or even not detected in outer city sites. DDTs were found at higher concentrations than HCHs and ranged between 0.18 and 4 ng/g dw (S5) and between 0.56 and 18 ng/g dw (S6). The parent compound, p,p′-DDT, could be detected only in low concentrations (up to 5 ng/g dw) and contributed with less than 30% to the sum of DDTs in sediment. The principal contributors of the ΣDDTs in sediment were p,p′-DDE, and p,p′-DDD. The o,p′-DDD and DDT isomers were minor contributors to the sum of DDT. PAHs were found at higher concentrations than DDTs and ranged between 6 and 36 ng/g dw (S5) and between 36 and 155 ng/g dw (S6). Fluoranthene was predominant (up to 40%), followed by phenantrene (up to 30%), naphthalene (up to 35%), and benzo-(g,h,i)-perylene (up to 23%). The saprobity index and the diatom index increased from springs to river mouth, indicating a decrease in the water quality, but within the limits of moderate pollution. The saprobity index varied between 1.99 at spring to 2.70 at mouth. The diatom index varied from 3.48 to 3.14. The species’ richness in phytoplankton has a less clear pattern along the river, but in general, it appears to be negatively influenced by pollution. At the level of biological consumer species, the analyses of the macroinvertebrates confirm the situation and the tendency shown with algae. In addition, the Shannon–Wiener index, the Pielou evenness index, and the McNaughton dominance index indicate a peculiar pattern: invertebrate communities appear to a have a more stable structure along the river, with visible shifts at springs and at river mouths. Water toxicity testing indicates low toxicity of river waters around the city of Iasi, with two notable exceptions: the point pollution at the domestic wastewater treatment discharge and at the old open-air deposit of domestic solid wastes. Another important result was that tested algae appeared to be more readily affected than tested cladoceran: EC₅₀ (percent effluent) was 16 in algae and 28 in cladocerans. The slope of toxic effect was also much steeper in cladocerans (6) than in algae (1.8), which means that the toxic effect is more sudden on the tested invertebrates than on the tested algae.

Discussion

Pollutant concentrations reported herein are lower or similar than those reported for the sediments by earlier studies (RIZA 2000; Dragan et al., Int J Environ Anal Chem 86:833–842, 2006). Ratios of individual PAH compounds indicate important pyrolytic inputs and suggest that PAHs in the area are derived from the combustion of fossil fuels. Biologically, the waters appear to be beta-mesosaprobic towards alpha-mesosaprobic according to the saprobic index classification and undergo moderate pollution according to the diatom index classification. Water quality decreases from springs to river mouths. Algal species richness index has a less clear pattern along the river. Water toxicity is low, but certain sources of point pollution require increased attention.

Conclusions

The water quality is better than expected, probably because of the drop in pollution intensity following the collapse of local agricultural and industrial activity following the fall of communism in 1989. Nevertheless, further studies will be needed to confirm and refine our results. While this study draws no strident alarm, it appeals for high attention, particularly because the economic activity in the area is expected to increase.

Recommendations and perspectives

Future close monitoring will be necessary for insuring compliance with the Water Framework Directive, and for refining standards and understanding of the local situation, but with relevance for the wider international community. On the basis of the situation described in the present study, we recommend that future studies dedicate specific efforts to point pollution and effluent toxicity, particularly around the city of Iasi. For a better understanding of pollution and its effects, we recommend pursuing the type of multidisciplinary investigations proposed by the present study: chemical, ecotoxicological, and ecological. We also recommend that new methods should be developed and/or refined, like the empirical determination of partitioning coefficients in water and soils, process-based toxicity methods in ecotoxicological assessments, searching for interactions between pollution, producers, and consumers in aquatic ecosystems. We also recommend preference for cheaper survey methods, as these will be more applicable locally.

     

Perfluorooctanoic acid and perfluorooctane sulfonate in the sediment of the Roter Main river, Bayreuth, Germany

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are widely distributed in aquatic ecosystems. Their sources are known but few studies about their accumulation potential in river sediments exist. The aim of this study is to assess the concentrations of PFOA and PFOS in sediments in relation to their levels in river water receiving effluent from a waste water treatment plant (WWTP). PFOS accumulates by a factor of about 40 relative to river water, PFOA only up to threefold. In contrast to previous suggestions, in this case the enrichment on sediment is not correlated to the total organic carbon contents.     

Monitoring Inter-Annual Variability Reveals Sources of Mercury Contamination in Clear Lake, California

Mercury (Hg) in the aquatic ecosystem of Clear Lake has been documented since the 1970s when fishes were found to have elevated levels of toxic methyl mercury (meHg). Mining practices at the Sulphur Bank Mercury Mine (active intermittently from 1872–1957) along the shoreline of Clear Lake included the bulldozing of waste rock and overburden ore into the shallow nearshore regions of the lake and the creation of steeply sloped piles of waste rock at the water's edge. This process, plus erosion of the waste rock piles, resulted in the accumulation of an estimated 100 metric tons of Hg in Clear Lake. A monitoring program to assess Hg in Clear Lake was established in 1992, and conducted continuously from 1994. Drought conditions in California had persisted for ca. 6 yrs prior to 1992, when the U.S. Environmental Protection Agency (USEPA) remediated the steeply sloped eroding waste rock piles, which appeared to reduce sediment Hg concentrations significantly. In April 1995, a white flocculent material was observed in Clear Lake adjacent to the mine and has been observed every year since, leading to the discovery of ongoing acid mine drainage (AMD), low pH fluids high in Hg and extremely high in sulfate. AMD is now believed to be the most likely cause of elevated meHg in Clear Lake. The discovery of this source of meHg production in Clear Lake, which will significantly influence remedial options, was only made possible by implementation of a diligent monitoring program.     

Parental care of replacement clutches in common terns (Sterna hirundo)

In long-lived seabirds with low annual reproductive output, the renesting decision after breeding failure is critical, and the parents have to weigh benefits of replacement clutches against possible future reproductive costs. In this study, we investigated factors influencing renesting decisions in common terns (Sterna hirundo) and compared aspects of breeding biology and body mass between two breeding attempts by the same pairs in each of 4 years of heavy losses due to predation. Renesting birds were characterized by early laying dates and by a high age. Among early breeders, high egg mass reduced the probability of renesting. A long relaying interval coincided with low mass of replacement eggs in one year, and short intervals with high egg mass in another. Further, egg mass decreased and relaying intervals increased the later the predation events occurred. Evidence of high levels of parental care of replacement clutches came from body mass data: female mass increase prior to egg laying was higher in the second attempt than in the first, whereas male mass was lower during the second courtship period than during the first. Male mass also affected relaying intervals and mass of replacement eggs. We conclude that common terns expend high levels of parental care of replacement clutches. Intrinsic factors related to individual quality (age, body condition) seemed most important for renesting decisions and for the degree of parental care, but foraging conditions seemed to have modifying effects. Received: 13 August 1999 / Received in revised form: 5 February 2000 / Accepted: 13 March 2000     

Perfluorooctanoic acid and perfluorooctane sulfonate released from a waste water treatment plant in Bavaria, Germany

Purpose

Perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), and precursors and derivatives thereof have been employed as surfactants and anti-adhesives. PFOA and PFOS are environmentally persistent and the discharge of municipal waste waters is one of the principal routes of these compounds into the aquatic environment. In a previous study, the concentrations of PFOA and PFOS in grab samples collected from the waste water treatment plant (WWTP) of Bayreuth, a city of 72,000 inhabitants in Bavaria, Germany, during two periods showed considerable variability. For a better estimate of average mass flows, the surfactants were monitored (five samplings) from 16 March to 18 May 2007. In a second campaign, river water receiving the WWTP effluent was sampled twice a day for five consecutive days.

Methods

Quantitative analysis was done by stable-isotope dilution, pre-cleaning, and pre-concentration by solid-phase extraction, and liquid chromatography followed by electrospray ionization/tandem mass spectrometry.

Results

The mass flows of PFOA and PFOS through the WWTP were determined. PFOA is fully discharged into the river, while about half of PFOS is retained in the sewage sludge. The average daily mass load of the river Roter Main by the WWTP of Bayreuth is about 1.2?±?0.5 g PFOA and 5?±?2 g PFOS, with variations of up to 140% within one day.

Conclusion

Overall, the total annual release to the rivers of Germany may be in the range of several hundred kilograms of PFOA and several tons of PFOS.     

Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (??PCB) congeners, dichlorodiphenyltrichloroethane (??DDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (??HCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ??PCB and HCB were highest in the southern sites, while ??DDT and ??HCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ??HCH increased at most sites, ??PCB and ??DDT in Sweden and Norway. In the Oystercatcher, HCB and ??HCH increased at more than the half of the sites, ??PCB, ??DDT and Hg at several German sites. In the terns, Hg, ??PCB and ??DDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ??HCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ??PCB and ??DDT exceeded the EcoQO in all or most years and sites. HCB and ??HCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.     

Preparation and X-ray structural characterization of further stereoisomers of 1,2,5,6,9,10-hexabromocyclododecane

Technical 1,2,5,6,9,10-hexabromocyclododecane (HBCD) consists largely of three diastereomers (α-, β-, and γ-HBCD) produced by the trans addition of bromine to cis,trans,trans-cyclododeca-1,5,9-triene (CDT). However, another seven diastereomers are theoretically possible and may be produced by trans addition of bromine across the double bonds of the other three isomers of 1,5,9-CDT. There are indications that small amounts of the minor HBCD isomers may be present in commercial HBCD mixtures or in products containing this brominated flame retardant (BFR). Such minor components may indeed derive from traces of other 1,5,9-CDTs in the cis, trans, trans starting material, however their formation may also be possible through isomerizations during the processing of this BFR or by bioisomerization subsequent to its release into the environment. Two of the seven additional diastereomers (δ- and ε-HBCD) were synthesized previously from trans,trans,trans-CDT. We now report the preparation of the remaining five diastereomers, ζ-, η-, and θ-HBCD from cis,cis,trans-CDT and ι- and κ-HBCD from cis,cis,cis-CDT, and their characterization by ¹H NMR spectroscopy and X-ray crystallography. The availability of these further diastereomers of HBCD should aid in determining if the minor isomers are present in commercial samples of this BFR, in products containing HBCDs, or in environmental samples. We have also carried out an X-ray crystal structure determination on ε-HBCD, so that crystal structures are now available for all 10 HBCD diastereomers.     

Temporal trend (1988-2008) of hexabromocyclododecane enantiomers in herring gull eggs from the German coastal region

Levels of α-, β-, and γ-hexabromocyclododecane (HBCD) were determined in pooled eggs from herring gulls (Larus argentatus) sampled on three bird sanctuaries near the German North Sea coast between 1988 and 2008 (Mellum and Trischen) and the German Baltic Sea coast between 1998 and 2008 (Heuwiese) and archived by the German Environmental Specimen Bank. Pressurized fluid extraction, gel permeation chromatography, and LC-MS/MS using ¹³C₁₂-labelled isotope standards and a chiral column were applied. α-HBCD was the dominating diastereomer and ranged between 3.7 and 107 ng g⁻¹ lw while β- and γ-HBCD were throughout close to LOQ. The highest α-HBCD concentration was found in eggs from Mellum sampled in the year 2000. Interestingly, HBCD in eggs from the three islands displayed similar time courses with levels increasing to a peak contamination around 2000 and decreasing levels ever since. Chiral signatures of α-HBCD in eggs differed among the islands but indicated a preferential enrichment of the first eluting enantiomer (−)-α-HBCD.     

Trace metal dynamics in an industrialized Brazilian river: A combined application of Zn isotopes, geochemical partitioning, and multivariate statistics

The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ^66/64Zn_JMC ≈ + 0.30‰) and anthropogenic (δ^66/64Zn_JMC ≈ + 0.15‰) end members. The lighter δ^66/64Zn_JMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.     

Are you an ambitious cyclist? Results of the cyclist profile questionnaire in Germany

Abstract

Objective: A number of studies have already grouped cyclists according to different aspects of their mobility behavior. This could be used e.g., to improve the bicycle infrastructure planning, to detect critical spots and, to reduce obstacles for cycling. This wide, preexisting, range of cyclist typologies usually concentrates on one or two influence factors and differs, content-wise, in both factors used, as well as, methodically. Based on existing cyclist typologies we extracted all possible influence factors to integrate them in one single questionnaire. The objective of this study, using an empirical, based approach, is to compare this typology of cyclists with existing ones, integrating all known influence factors of recent studies.

Methods: To address these issues, we conducted a Germany-wide online survey on cycling behavior, covering all relevant aspects we derived from both literature and especially, former cyclist typology studies including: social factors; the impact of environmental, individual; and route factors; as well as motives. The main goal was to identify distinct types of cyclists, and describe them as detailed as possible. The heterogeneous sample included a total of 10,294 responses.

Results: Using factor and cluster analyses, a multidimensional typology with four groups of cyclists was derived which were interpreted as: ambitious, functional, pragmatic, and passionate cyclists. In addition, socio-economic factors, cyclist’s motivation, and crash history were analyzed.

Conclusion: The results produced by grouping different characteristics of cyclists can lead to policy recommendations or communal bicycle traffic planning. Policy planners can estimate reactions of the different types on interventions and adjust their decisions which can serve to support already passionate cyclists or, encourage normally under-represented infrequent cyclists to cycle more. The extent of perceived safety plays here an important role in the classification, e.g., the handling of high-risk areas for crashes.