Freshwater Ulva (Chlorophyta) as a bioaccumulator of selected heavy metals (Cd, Ni and Pb) and alkaline earth metals (Ca and Mg)

We analyzed the ability of freshwater taxa of the genus Ulva (Ulvaceae, Chlorophyta) to serve as bioindicators of metal in lakes and rivers. Changes in heavy metal (Ni, Cd and Pb) and alkaline earth metal (Ca and Mg) concentrations in freshwater Ulva thalli were investigated during the period from June to August 2010. The study was conducted in two ecosystems in Western Poland, the Malta lake (10 sites) and the Nielba river (six sites). Three components were collected for each sample, including water, sediment and Ulva thalli. The average concentrations of metals in the water sample and in the macroalgae decreased in the following order: Ca > Mg > Ni > Pb > Cd. The sediment revealed a slightly altered order: Ca > Mg > Pb > Ni > Cd. Ca and Mg were found at the highest concentrations in thalli due to the presence of carbonate on its surface. Among the examined heavy metals in thalli, Ni was in the highest concentration, and Cd found in the lowest concentration. There were statistically significant correlations between the levels of metals in macroalgae, water and sediment. Freshwater populations of Ulva exhibited a greater efficiency to bioaccumulate nickel as compared to species derived from marine ecosystems.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

Constructed wetlands as a component of the agricultural landscape: mitigation of herbicides in simulated runoff from upland drainage areas

Constructed wetlands are a recommended practice for buffering pollutant source areas and receiving waters. A wetland consisting of a sediment trap and two treatment cells was constructed in a Mississippi Delta lake watershed. A 3-h simulated runoff event was initiated (2003) to evaluate fate and transport of atrazine and fluometuron through the wetland. Water samples were collected during a runoff simulation and then afterward at selected intervals for 21 d, and analyzed for the herbicides. Breakthrough patterns for herbicide concentrations in water samples during the first 20 h after simulated runoff showed peak concentrations in the first 6 h, with gradual tailing as the herbicide pulse was diluted in the second, excavated (deeper) cell. Atrazine and fluometuron concentrations in the first (shallower, non-excavated) cell averaged 12- and 20-fold greater, respectively, than those in the second cell following simulated runoff, indicating entrapment in the first cell. Atrazine and fluometuron concentrations in the shallower cell decreased 32% and 22%, respectively, 9 d following simulated runoff, indicating either degradation or sorption to soil or wetland flora. In the excavated cell, concentrations were even lower, and atrazine declined more rapidly than fluometuron. Results indicate constructed wetlands can improve downstream water quality though sequestration or processing of pollutants.     

Influence of aggregated particles on biodegradation activities for dimethylarsinic acid (DMA) in Lake Kahokugata

Aquatic arsenic cycles mainly depend on microbial activities that change the arsenic chemical forms and influence human health and organism activities. The microbial aggregates degrading organic matter are significantly related to the turnover between inorganic arsenic and organoarsenic compounds. We investigated the effects of microbial aggregates on organoarsenic mineralization in Lake Kahokugata using lake water samples spiked with dimethylarsinic acid (DMA). The lake water samples converted 1 μmol L⁻¹ of DMA to inorganic arsenic for 28 d only under anaerobic and dark conditions in the presence of microbial activities. During the DMA mineralization process, organic aggregates >5.0 μm with bacterial colonization increased the densities. When the organic aggregates >5.0 μm were eliminated from the lake water samples using filters, the degradation activities were reduced. DMA in the lake water would be mineralized by the microbial aggregates under anaerobic and dark conditions. Moreover, DMA amendment enhanced the degradation activities in the lake water samples, which mineralized 50 μmol L⁻¹ of DMA. The DMA-amended aggregates >5.0 μm completely degraded 1 μmol L⁻¹ of DMA with a shorter incubation time of 7 d. The supplement of KNO₃ and NaHCO₃ to lake water samples also shortened the DMA-degradation period. Presumably, the bacterial aggregates involved in the chemical heterotrophic process would contribute to the DMA-biodegradation process in Lake Kahokugata, which is induced by the DMA amendment.     

PCBs in sediments of the Great Lakes--distribution and trends, homolog and chlorine patterns, and in situ degradation

A region-wide data analysis on polychlorinated biphenyls (PCBs) in the sediment of the Great Lakes reveals a total accumulation of approximately 300 ± 50 tonnes, representing a >30% reduction from the 1980s. Evidence of in situ degradation of sediment PCB was found, with estimated t_1/2 of 11 and 17 years, at two open water locations in Lake Ontario. The relative abundance of heavy homologs as well as para-chlorines decreases with increasing depth, while the opposite is true for medium and light homologs and ortho-chlorines. In Lake Michigan, the vertical pattern features enrichment of heavier congeners and reduction of ortho-chlorines in deeper sediment layers, opposite to the trend in Lake Ontario. PCBs decrease log-linearly with increasing latitude and longitude. Air deposition of PCBs to lake sediment decreases at about 0.077 ng cm⁻² yr⁻¹ per degree latitude (N) for the geographic region extending from the Great Lakes to within the Arctic Circle.     

Partitioning behaviour of perfluorinated alkyl contaminants between water, sediment and fish in the Orge River (nearby Paris, France)

This paper reports on the partitioning behaviour of 15 perfluorinated compounds (PFCs), including C₄-C₁₀ sulfonates and C₅-C₁₄ carboxylic acids, between water, sediment and fish (European chub, Leuciscus cephalus) in the Orge River (nearby Paris). Total PFC levels were 73.0 ± 3.0 ng L⁻¹ in water and 8.4 ± 0.5 ng g⁻¹ in sediment. They were in the range 43.1-4997.2 ng g⁻¹ in fish, in which PFC tissue distribution followed the order plasma > liver > gills > gonads > muscle. Sediment-water distribution coefficients (log K_d) and bioaccumulation factors (log BAF) were in the range 0.8-4.3 and 0.9-6.7, respectively. Both distribution coefficients positively correlated with perfluoroalkyl chain length. Field-based biota-sediment accumulation factors (BSAFs) are also reported, for the first time for PFCs other than perfluorooctane sulfonate. log BSAF ranged between −1.3 and 1.5 and was negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids.     

Sediment quality guidelines for copper and zinc for filter-feeding estuarine oysters?

Sediment quality guidelines (SQGs) assess the ability of bottom sediment to sustain healthy infauna and water quality guidelines (WQGs) provide protection for a designated percentage of aquatic species. Filter-feeding marine species, e.g. oysters and mussels, acquire food from particles in the water column and protection of these animals is not provided by SQGs or WQGs. The current work investigated the relationship between metal (Cu, Zn) concentrations in total and fine-fraction (<62.5 μm) surficial sediment digested in a range of acids and chelating agents and oyster tissue metal concentrations. A strong correlation between oyster tissue Cu and Zn concentrations and fine-fraction surficial sediment digested in 1 M HCl provided a sedimentary guideline which predicted tissue metal concentrations in oysters and established a level (<45 μg g⁻¹ and <1000 μg g⁻¹, respectively) for protecting oysters from exceeding human consumption levels (70 μg g⁻¹ and 1000 μg g⁻¹, respectively).     

Removal mechanisms and fate of insecticides in constructed wetlands

Constructed wetlands (CWs), along with other vegetative systems, are increasingly being promoted as a mitigation practice to treat non-point source runoff to reduce contaminants such as pesticides. However, studies so far have mostly focused on demonstrating contaminant removal efficiency. In this study, using two operational CWs located in the Central Valley of California, we explored the mechanisms underlying the removal of pyrethroids and chlorpyrifos from agricultural runoff water, and further evaluated the likelihood for the retained pesticides to accumulate within the CWs over time.In the runoff water passing through the CWs, pyrethroids were associated overwhelmingly with suspended solids >0.7 μm, and the sorbed fraction accounted for 38-100% of the total concentrations. The derived K_d values for the suspended solids were in the order of 10⁴-10⁵, substantially greater than those reported for bulk soils and sediments. Distribution of pyrethroids in the wetland sediments was found to mimic organic carbon distribution, and was enriched in large particles that were partially decomposed plant materials, and clay-size particles (<2 μm). Retention of suspended particles, especially the very large particles (>250 μm) and the very fine particles, is thus essential in removing pyrethroids and chlorpyrifos in CWs. Under flooded and anaerobic conditions, most pyrethroids and chlorpyrifos showed moderate persistence, with DT₅₀ values between 106-353 d. However, the retained pyrethroids were very stable in dry and aerobic sediments between irrigation seasons, suggesting a possibility for accumulation over time. Therefore, the long-term ecological risks of CWs should be further understood before their wide adoption.     

Mass balance modeling to elucidate historical and continuing sources of dioxin into an urban estuary

Polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) are typically found in sediment, water and tissue as in the case of the Houston Ship Channel and Upper Galveston Bay (HSC–UGB) in Texas studied in this research. While hydrodynamic and fate and transport models are important to understand dioxin distribution in the various media, it is difficult to assimilate modeling results into a decision framework without appropriate tools that can aid in the interpretation of the simulated data. This paper presents the development of a mass-balance modeling tool linked to RMA2 and WASP models of the HSC–UGB system for 2002–2005. The mass-balance tool was used to aggregate modeling results spatially and temporally and estimate the relative contribution of sediments to dioxin loading into the Channel in comparison to runoff, deposition, and permitted effluent discharges. The total sediment associated-dioxin load into the system calculated using the mass balance model was 2.34 × 10⁷ ng d⁻¹ (almost 86% of the toxic equivalent load), and the re-deposited load to the sediment from the water column was 1.48 × 10⁷ ng-TEQ d⁻¹, such that 8.6 × 10⁶ ng-TEQ d⁻¹ or approximately 69% of the average daily dioxin flux is transported between model segments as sediment. The external loads to the system contribute approximately 3.83 × 10⁶ ng-TEQ d⁻¹, a value that is an order of magnitude smaller when compared to the contribution from sediment. These findings point to the need for sediment remediation strategies that take into account the spatial locations within the system that serve as sediment sources to dioxin in the water column.     

Free atmospheric phosphine concentrations and fluxes in different wetland ecosystems, China

Atmospheric phosphine (PH₃) fluxes from typical types of wetlands and PH₃ concentrations in adjacent atmospheric air were measured. The seasonal distribution of PH₃ in marsh and paddy fields were observed. Positive PH₃ fluxes are significantly related to high air temperature (summer season) and increased vegetation. It is concluded that vegetation speeds up the liberation of PH₃ from soils, while water coverage might function as a diffusion barrier from soils or sediments to the atmosphere. The concentrations of atmospheric PH₃ (ng m⁻³) above different wetlands decrease in the order of paddy fields (51.8 ± 3.1) > marsh (46.5 ± 20.5) > lake (37.0 ± 22.7) > coastal wetland (1.71 ± 0.73). Highest atmospheric PH₃ levels in marsh are found in summer. In paddy fields, atmospheric PH₃ concentrations in flourishing stages are higher than those in slowly growing stages.     

Mitigation of two pyrethroid insecticides in a Mississippi Delta constructed wetland

Constructed wetlands are a suggested best management practice to help mitigate agricultural runoff before entering receiving aquatic ecosystems. A constructed wetland system (180 m × 30 m), comprising a sediment retention basin and two treatment cells, was used to determine the fate and transport of simulated runoff containing the pyrethroid insecticides lambda-cyhalothrin and cyfluthrin, as well as suspended sediment. Wetland water, sediment, and plant samples were collected spatially and temporally over 55 d. Results showed 49 and 76% of the study's measured lambda-cyhalothrin and cyfluthrin masses were associated with vegetation, respectively. Based on conservative effects concentrations for invertebrates and regression analyses of maximum observed wetland aqueous concentrations, a wetland length of 215 m × 30 m width would be required to adequately mitigate 1% pesticide runoff from a 14 ha contributing area. Results of this experiment can be used to model future design specifications for constructed wetland mitigation of pyrethroid insecticides.     

Metal sorption by peat and algae treated peat: kinetics and factors affecting the process

The article presents a new approach that can be used for the purification of water contaminated by heavy metals. The treatment of peat with microalgae showed to be an effective way of increasing metal uptake by peat. Metal sorption was studied for a multimetal solution containing Cu, Cd, Ni, Zn, Cd, and Pb. Cu and Pb were found to be the metals having the highest affinity to peat. Water hardness has a strong effect on the uptake of borderline metals (Cd, Ni, Zn, Cd) from a solution. The use of algae for peat treatment resulted in less time to reach an equilibrium (24 h vs. 72 h for pure peat), and the effect of water hardness (Ca²⁺) on metal uptake was considerably reduced. Both peat and algal-treated peat were able to take up metals from rather acidic solutions (pH 3.0). pH had less influence on the metal uptake compared with water hardness. The affinity of heavy metals to peat was the following: Pb > Cu > Ni > Cd > Zn > Co. It slightly changed to Pb > Cu > Ni > Cd ≈ Co ≈ Zn when the combined sorbent, peat treated with microalga, was applied.     

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (log K_d) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K_d or K_OC) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK_d for size fractions of SL and ST did not follow the order: clay > silt > sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.     

Vaporization of heavy metals during thermal treatment of model solid waste in a fluidized bed incinerator

This paper investigated the volatilization behavior of heavy metals during thermal treatment of model solid waste in a fluidized bed reactor. Four metal chlorides (Cd, Pb, Cu and Zn) were chosen as metal sources. The influence of redox conditions, water and mineral matrice on heavy metal volatilization was investigated. In general, Cd shows significant vaporization especially when HCl was injected, while Cu and Pb vaporize moderately and Zn vaporization is negligible. Increasing oxygen concentration can lower heavy metal vaporization. Heavy metal interactions with the mineral matter can result in the formation of stable metallic species thus playing a negative effect on their behavior. However, HCl can promote the heavy metal release by preventing the formation of stable metallic species. The chemical sorption (either physical or chemical) inside the pores, coupled with the internal diffusion of gaseous metal species, may also control the vaporization process. With SO₂ injected, Cd and Pb show a higher volatility as a result of SO₂ reducing characteristics. From the analysis, the subsequent order of heavy metal volatility can be found: Cd > Cu ? Pb ? Zn.     

Partitioning of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) between water and sediment

Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (K_OC) decreased in the following order: PFOSA (log K_OC = 4.1 ± 0.35 cm³ g⁻¹) > PFOS (3.7 ± 0.56 cm³ g⁻¹) > PFOA (2.4 ± 0.12 cm³ g⁻¹). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate.     

Occurrence and effects of tire wear particles in the environment--a critical review and an initial risk assessment

This review summarizes the existing knowledge on the occurrence of tire wear particles in the environment, and their ecotoxicological effects. A meta-analysis on tire components in the environment revealed that tire wear particles are present in all environmental compartments, including air, water, soils/sediments, and biota. The maximum Predicted Environmental Concentrations (PECs) of tire wear particles in surface waters range from 0.03 to 56 mg l⁻¹ and the maximum PECs in sediments range from 0.3 to 155 g kg⁻¹ d.w. The results from our previous long-term studies with Ceriodaphnia dubia and Pseudokirchneriella subcapitata were used to derive Predicted No Effect Concentrations (PNECs). The upper ranges for PEC/PNEC ratios in water and sediment were >1, meaning that tire wear particles present potential risks for aquatic organisms. We suggest that management should be directed towards development and production of more environmentally friendly tires and improved road runoff treatment.     

晋江西溪流域茶园降雨径流产污特征

在野外模拟降雨条件下,开展了晋江西溪流域茶园和裸地的径流产沙及氮磷养分流失过程对比实验,研究结果表明,在相同降雨强度下,3种下垫面径流和产沙量顺序均为:裸地＞2年茶园＞4年茶园,径流量与产沙量之间呈显著正相关.对地表径流水相而言,2年茶园、4年茶园和裸地的TN流失量分别为:461.29、129.38和107.86 mg/m2;NO3-N流失量分别为:286.42、98.58和103.00 mg/m2,均占TN流失量的60％以上;NH4-N流失量分别为:48.67、16.19和4.42 mg/m2;Tp流失量分别为:34.71、16.47和23.88 mg/m2.对径流泥沙相而言,2年茶园、4年茶园和裸地的TN流失量分别为:379.28、44.81和747.16 mg/m2,占流失总量的比重在25.72％～87.93％之间;TP流失量分别为:27.94、4.17和58.85 mg/m2,占流失总量的比重在53.42％ ～68.36％之间.茶园的N、P主要随径流流失,而裸地以泥沙迁移为主.这说明茶叶种植具有一定的水土保持效应,且种植年限较长的茶园可显著减少随径流泥沙进入水体中的N、P元素.     

Risk assessment of xenoestrogens in a typical domestic sewage-holding lake in China

Release of domestic sewage leads to accumulation of xenoestrogens in holding waters, especially in closed or semi-enclosed waters such as lakes. In the study, the occurrence, distribution, estrogenic activity and risk of eight xenoestreogens were evaluated in Lake Donghu, China. Nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) were identified as the main xenoestrogens ranging from tens of ng L⁻¹ (in the surface water) or ng g⁻¹ dw (in the suspended particles and sediment) to tens of μg L⁻¹ or μg g⁻¹ dw. The sum of 17β-estradiol equivalents (∑EEQs) ranged from 0.32 to 45.02 ng L⁻¹ in the surface water, 0.53 to 71.86 ng g⁻¹ dw in the suspended particles, and 0.09 to 24.73 ng g⁻¹ dw in the sediment. Diethylstilbestrol (DES) was determined as the main contributor to ∑EEQs followed by NP. The risk assessment showed a higher risk in the surface water than in the suspended particles and sediment in such domestic sewage-holding lake.     

Widespread waterborne pollution in central Swedish lakes and the Baltic Sea from pre-industrial mining and metallurgy

Metal pollution is viewed as a modern problem that began in the 19th century and accelerated through the 20th century; however, in many parts of the globe this view is wrong. Here, we studied past waterborne metal pollution in lake sediments from the Bergslagen region in central Sweden, one of many historically important mining regions in Europe. With a focus on lead (including isotopes), we trace mining impacts from a local scale, through a 120-km-long river system draining into Mälaren - Sweden's third largest lake, and finally also the Baltic Sea. Comparison of sediment and peat records shows that pollution from Swedish mining was largely waterborne and that atmospheric deposition was dominated by long-range transport from other regions. Swedish ore lead is detectable from the 10th century, but the greatest impact occurred during the 16th-18th centuries with improvements occurring over recent centuries, i.e., historical pollution > modern industrial pollution.     

Temporal variability in dynamic and colloidal metal fractions determined by high resolution in situ measurements in a UK estuary

In recent environmental legislation, such as the Water Framework Directive in the European Union (WFD, 2000/60/EC), the importance of metal speciation and biological availability is acknowledged, although analytical challenges remain. In this study, the Voltammetric In situ Profiler (VIP) was used for high temporal resolution in situ metal speciation measurements in estuarine waters. This instrument simultaneously determines Cd, Cu and Pb species within a size range (ca. <4 nm) that is highly relevant for uptake by organisms. The colloidal metal fraction can be quantified through a combination of VIP measurements and analyses of total dissolved metal concentrations.VIP systems were deployed over tidal cycles in a seasonal study of metal speciation in the Fal Estuary, southwest England. Total dissolved concentrations were 4.97-315 nM Cu, 0.13-8.53 nM Cd and 0.35-5.75 nM Pb. High proportions of Pb (77 ± 17%) and Cu (60 ± 25%) were present as colloids, which constituted a less important fraction for Cd (37 ± 30%). The study elucidated variations in the potentially toxic metal fraction related to river flow, complexation by organic ligands and exchanges between dissolved and colloidal phases and the sediment. Based on published toxicity data, the bioavailable Cu concentrations (1.7-190 nM) in this estuary are likely to severely compromise the ecosystem structure and functioning with respect to species diversity and recruitment of juveniles. The study illustrates the importance of in situ speciation studies at high resolution in pursuit of a better understanding of metal (bio)geochemistry in dynamic coastal systems.