Cumulative and Residual Effects of Repeated Sewage Sludge Applications: Forage Productivity and Soil Quality Implications in South Florida,USA (9 pp)

Background, Aim and Scope The cow-calf (Bos taurus) industry in subtropical United States and other parts of the world depends almost totally on grazed pastures. Establishment of complete, uniform stand of bahiagrass (BG) in a short time period is important economically. Failure to obtain a good BG stand early means increased encroachment of weeds and the loss of not only the initial investment costs, but production and its cash value. Forage production often requires significant inputs of lime, N fertilizer, and less frequently of P and K fertilizers. Domestic sewage sludge or biosolids, composted urban plant debris, waste lime, phosphogypsum, and dredged materials are examples of materials that can be used for fertilizing and liming pastures. Perennial grass can be a good choice for repeated applications of sewage sludge. Although sewage sludge supply some essential plant nutrients and provide soil property-enhancing organic matter, land-application programs still generate some concerns because of possible health and environmental risks involved. The objectives of this study were to evaluate the cumulative and residual effects of repeated applications of sewage sludge on (i) bahiagrass (BG, Paspalum notatum Flügge) production over years with (1997–2000) and without (2001–2002) sewage sludge applications during a 5-yr period, and (ii) on nutrients status of soil that received annual application of sewage sludge from 1997 to 2000 compared with test values of soils in 2002 (with no sewage sludge application) in South Florida.Methods The field experiment was conducted at the University of Florida Agricultural Research and Education Center, Ona, FL (27o26’N, 82o55’W) on a Pomona fine sandy soil. With the exception of the control, BG plots received annual sewage sludge and chemical fertilizers applications to supply 90 or 180 kg total N ha–1 yr–1 from 1997 to 2000. Land application of sewage sludge and fertilizer ceased in 2001 season. In early April 1998, 1999, and 2000, plots were mowed to 5-cm stubble and treated with the respective N source amendments. The experimental design was three randomized complete blocks with nine N-source treatments: ammonium nitrate (AMN), slurry biosolids of pH 7 (SBS7), slurry biosolids of pH 11 (SBS11), lime-stabilized cake biosolids (CBS), each applied to supply 90 or 180 kg N ha–1, and a nonfertilized control (Control). Application rates of sewage sludge were calculated based on the concentration of total solids in materials as determined by the American Public Health Association SM 2540G method and N in solids. The actual amount of sewage sludge applications was based on the amount required to supply 90 and 180 kg N ha–1. Sewage sludge materials were weighed in buckets and uniformly applied to respective BG plots. Soil samples were collected in June 1997, June 1999, and in June 2002 from 27 treatment plots. In 1997 and 1999, soil samples were collected using a steel bucket type auger from the 0- to 20-, 20- to 40-, 40- to 60-, and 60- to 100-cm soil depths. Forage was harvested on 139, 203, 257, and 307 day of year (DOY) in 1998; 125, 202, 257, and 286 DOY in 1999; 179, 209, 270, and 301 DOY in 2000; and on 156 and 230 DOY in 2002 (no sewage sludge applications) to determine the residual effect of applied sewage sludge following repeated application. Forage yield and soils data were analyzed using analysis of variance (PROC ANOVA) procedures with year and treatment as the main plot and sub-plot, respectively. As a result of significant year effects on forage yield, data were reanalyzed annually (i.e., 1998, 1999, 2000, and 2002).Results and Discussion All sewage sludges used in this study were of class B in terms of USEPA’s pathogens and pollutant concentration limit. Pathogen and chemical composition of the class B sewage sludge that were used in the study were all in compliance with the USEPA guidelines. The liquid sludge (SBS11) had the lowest fecal coliform counts (0.2 x 106 CFU kg–1) while the cake sewage sludge (CBS) had the greatest coliform counts of 178 x 106 CFU kg–1. The fecal coliform counts for SBS7 was about 33 x 106 CFU kg–1. Average soil test values in June 2002 exhibited: i) decrease in TIN (NO3-N + NH4-N), TP, K, Ca, Mg, Mn, and Fe; and ii) slight increase in Zn and Cu when compared with the June 1997 soil test results. The overall decrease in soil test values in 2002 might be associated with nutrient cycling and plant consumption. Although the average BG forage yield in 2002 (2.3 ± 0.7 Mg ha–1) was slightly lower than in 2000 (3.5 ± 1.2 Mg ha–1), yield differences in 2002 between the control (1.2 + 0.2 Mg ha–1) and treated plots (2.3 ± 0.5 Mg ha–1 to 3.3 ± 0.6 Mg ha–1) were indicative of a positive residual effect of applied sewage sludge. This study has shown that excessive build up of plant nutrients may not occur in beef cattle pastures that repeatedly received sewage sludge while favoring long-term increased forage yield of BG. All sources of N (sewage sludge and AMN) gave better forage production than the unfertilized control during years with sewage sludge application (1997–2000) and also during years with no sewage sludge application (2001–2002). The favorable residual effects of applied sewage sludge in 2002 may have had received additional boost from the amount of rainfall in the area.Conclusions Repeated applications of sewage sludge indicate no harmful effects on soil quality and forage quality. Our results support our hypothesis that repeated land application of sewage sludge to supply 90 and 180 kg N ha–1 would not increase soil sorption for nutrients and trace metals. Results have indicated that the concentrations of soil TIN and TP declined by almost 50% in plots with different nitrogen sources from June 1997 to June 2002 suggesting that enrichment of nitrogen and phosphorus is insignificant. The concentrations of soil nitrogen and phosphorus in 2002 following repeated application of sewage sludge were far below the contamination risk in the environment. The residual effect of these sewage sludge over the long term can be especially significant in many areas of Florida where only 50% of the 1 million ha of BG pastures are given inorganic nitrogen yearly.Recommendation and Outlook Successive land application of sewage sludge for at least three years followed by no sewage sludge application for at least two years may well be a good practice economically because it will boost and/or maintain sustainable forage productivity and at the same time minimize probable accumulation of nutrients, especially trace metals. Consecutive applications of sewage sludge may result in build up of some trace metals in some other states with initial high metallic content, but in this study, no detrimental effects on soil chemical properties were detected. The possibilities for economically sound application strategies are encouraging, but more and additional research is required to find optimal timing and rates that minimizes negative impacts on soil quality in particular or the environment in general. For proper utilization of sewage sludge, knowledge of the sewage sludges’ composition, the crop receiving it, are absolutely crucial, so that satisfactory types and rates are applied in an environmentally safe manner. There is still much to be learned from this study and this investigation needs to continue to determine whether the agricultural and ecological objectives are satisfied over the longer term.     

Investigation of the characteristics of the reflectivity of clouds

This paper investigates some of the reflectivity characteristics that clouds (when modelled as solid bodies) must exhibit to be compatible with observations that the reflecting surface of a cloud (i) appears almost equally bright across its face, (ii) is brightest when the cloud is opposite to the Sun but decreases in brightness as the cloud moves to other positions and (iii) increases in brightness with increasing optical thickness of the cloud in the observer's line of sight. These observations, respectively, are shown to imply that the peak value of the bidirectional total reflectivity from a cloud surface (i) increases in inverse proportion to the cosine of the angle between the Sun and the normal to the cloud surface, as the incident angle increases, (ii) appears to be directed back in the direction of the incident radiation, and (iii) increases as optical thickness of the cloud in the observer's line of sight increases. The results could have application in many fields (e.g. modelling diffuse radiance distributions for cloudy skies).     

Isolation of the stable fraction (the core) of the humic acid

Humic acid consists of a recalcitrant (unhydrolysed fraction) (the core) and labile (hydrolysable fraction) fraction. Core-humic acid (core-HA) isolation was performed by treating source material with apolar and polar solvents (organic solvents+acid hydrolysis) before alkaline extraction. Leonardite, soil Ah horizont and dry blood were chosen for this study because of their different origin and degree of humification. Chemical analysis (elemental analysis, total acidity, E(4):E(6)), spectroscopic analysis (DRIFT and (1)H NMR), and complete mass balance were used to investigate the effect of purifying humic acids. The results obtained showed that purification produced a slight modification of Leonardite humic acids as was expected for these highly humified organic matrices. On the other hand, about 500 g kg(-1) of soil humic acids were lost by purification. The fractions lost mainly consisted of carbohydrates. Dry blood showed the presence of humic acids that contrasted with its origin, thus indicating the limitations of the common analytical methods used for HA extraction. Nevertheless, in practice, purification caused the complete disappearance (914 g kg(-1) of HA was lost) of these HAs. The results obtained in this work suggest that the HA fraction isolated (named core-HA) effectively represents the HA structure proposed by the existing literature, since the purification proposed was able to eliminate the adsorbed organic molecules (interference materials) coating the HA structure.     

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.     

Effects of sensitizers on the photodegradation of the systemic fungicide triadimenol

The photochemical behaviour of triadimenol (1) under various conditions has been examined. Significant degradation is obtained only in the presence of electron-acceptor sensitizers as 9,10-dicyanoanthracene or 2,4,6-triphenylpyrylium tetrafluoroborate, and long irradiation times are required. 1H-1,2,4-Triazole (2), 4-chlorophenyl formate (3), 4-chlorophenol (4), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (5), 4-chlorophenyl 2,2-dimethylpropanoate (6) and 4-chlorobenzoic acid (7) were identified as photoproducts by NMR and GC-MS.     

Effects of perfluoroalkyl acids on the function of the thyroid hormone and the aryl hydrocarbon receptor

Perfluoroalkyl acids (PFAAs) are perfluorinated compounds that widely exist in the environment and can elicit adverse effects including endocrine disruption in humans and animals. This study investigated the effect of seven PFAAs on the thyroid hormone (TH) system assessing the proliferation of the 3,3′,5-triiodo-l-thryonine (T3)-dependent rat pituitary GH3 cells using the T-screen assay and the effect on the aryl hydrocarbon receptor (AhR) transactivation in the AhR-luciferase reporter gene bioassay. A dose-dependent impact on GH3 cells was observed in the range 1?×?10^?9–1?×?10^?4 M: seven PFAAs (perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA)) inhibited the GH3 cell growth, and four PFAAs (PFOS, PFHxS, PFNA, and PFUnA) antagonized the T3-induced GH3 cell proliferation. At the highest test concentration, PFHxS showed a further increase of the T3-induced GH3 growth. Among the seven tested PFAAs, only PFDoA and PFDA elicited an activating effect on the AhR. In conclusion, PFAAs possess in vitro endocrine-disrupting potential by interfering with TH and AhR functions, which need to be taken into consideration when assessing the impact on human health.     

Factors influencing the total mercury and methyl mercury in the hair of the fishermen of Kuwait

Total and methyl mercury (MeHg) levels in the hair of fishermen are described anticipating that they represent the critical group for dietary exposure. One-hundred human hair samples were collected from fishermen (Egyptians: age range 25-60), living in Doha Fishing Village, Kuwait. Thirty-five additional samples were taken from a control group working in a local construction company (age range 26-35). Overall mean concentrations in the hair of the population of fishermen are 4.181+/-3.220 and 4.025+/-3.130 microg g(-1) for total and MeHg, respectively. The equivalent values for the control are 2.617+/-1.404 and 2.556+/-1.391 microg g(-1) for total and MeHg, respectively. MeHg concentrations are strongly correlated to those of total Hg ( [Formula: see text], [Formula: see text] ) and MeHg concentrations in human hair are unrelated to age and duration of residence in Kuwait but show a positive correlation with the quantity of fish consumed. Levels of Hg in hair also show a tendency to increase in those who prefer to eat the entire fish, including the heads. In general, the concentrations of total and MeHg in fishermens' hair are twice the WHO 'normal' level (2.0 microg g(-1)) but are still less than the WHO threshold level (10.0 microg g(-1)). The results also show that grey hair contains undetectable amounts of Hg and therefore does not reflect individual exposure to this contaminant.     

Modeling the reaction kinetics of Fenton's process on the removal of atrazine

The degradation of pesticide, atrazine (ATZ), 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine, by Fenton's reagent (FR) was investigated as a function of reagents' concentrations and ratios in a batch reactor. The degradation of ATZ was effectively achieved by hydroxyl radicals, which were generated in the FR process. The decay rates of ATZ and the oxidation capacities of FR were found to depend on the concentrations of hydrogen peroxide and ferrous ion. The removal kinetics of ATZ are initiated by a rapid decay and then followed by a much slower one. After an extended reaction time (5-10 min), the reactions ceased because the Fe(II) and H(2)O(2) were consumed and would be deactivated in the process. A mathematical model was successfully developed to describe the two-stage reaction kinetics by using two simple but critical parameters: the initial ATZ decay rate and the final oxidation capacity of Fenton's process. In general, higher [Fe(II)] or H(2)O(2) concentrations result in faster initial decay rate and higher oxidation capacity. However, the oxidation capacity is more sensitive to the initial [Fe(II)] due to the presence of side reactions as discussed in the paper.     

Setting the stage for the review of the international estimate of short-term intake (IESTI) equation

ABSTRACT

In the framework of setting Maximum Residue Limits (MRLs) for pesticides, both chronic and acute health risks to consumers arising from the long-term and short-term dietary exposure to pesticide residues have to be assessed. The current internationally harmonized approach for assessing the acute dietary exposure is based on deterministic methods for calculating the IESTI (International Estimate of Short-Term Intake). Recently, it became apparent that the IESTI approach needs a revision in the light of new scientific and political aspects. The main reasons that require this review were the lack of an international harmonization of the methodology which implies trade barriers as well as difficulties in risk communication concerning the public trust in regulatory systems. The most recent milestone in the scientific debate on a possible revision of the IESTI equation was an international scientific workshop held in Geneva in September 2015. The main objectives of this meeting were the re-evaluation, and where possible, the international harmonization of the input parameters for the IESTI equations as well as the equations themselves. The main recommendations from the workshop were (i) to replace the highest residue and supervised trials median residue with the maximum residue limit (MRL), (ii) to use a standard variability factor of three, (iii) to derive the P97.5 large portion value from the distribution of consumption values of dietary surveys expressed as kg food/kg bw/d, and (iv) to remove the commodity unit weight from the equations. In addition, the application of conversion factors and processing factors was addressed. On the initiative of the (World Health Organization) WHO Collaborating Centre on Chemical Food Safety at the National Institute for Public Health and the Environment (RIVM), the Netherlands, an international working group with members from the French Agency for Food, Environmental and Occupational Health and Safety, France (ANSES), Australian Pesticides and Veterinary Medicines Authority, Australia (APVMA), German Federal Institute for Risk Assessment, Germany (BfR), Chemical Regulation Division, the United Kingdom (CRD), European Food Safety Authority (EFSA), and RIVM, the Netherlands was formed after the IESTI workshop to conduct a comprehensive impact assessment of the proposed changes of the IESTI equations.     

The influence of the season and the biotic factors on the cytosolic metal concentrations in the gills of the European chub (Leuciscus cephalus L.)

The influence of the season and the biotic factors (age and gill mass) on metal and protein levels in the gill cytosol of the young chubs (2 and 3 years old) was studied in Sava River in autumn 2005 and spring 2006. The obtained results are the first reported cytosolic concentrations of five metals and proteins for the chub gills. The average levels in autumn and spring, respectively, for total cytosolic proteins were 11.2 and 19.9 mg ml(-1), for Zn 6.3 and 10.3 microg ml(-1), for Fe 3.9 and 9.6 microg ml(-1), for Cu 68.4 and 79.0 ng ml(-1), for Mn 55.0 and 63.5 ng ml(-1), and for Cd 2.9 and 3.6 ng ml(-1). The influence of the gill mass on both the protein and the metal levels was observed, but it was seasonally dependent. In autumn, positive correlations were obtained between the gill mass and four parameters (total proteins, Mn, Zn and Fe), and negative with Cu. Contrary, in spring, even negative correlations of total proteins and some metals with the gill mass were observed. The proposed explanation for the different dependence of metal levels on the gill mass in autumn and spring was the seasonal difference in feeding intensity and metabolic rate, with presumably faster metabolism and water filtration through gills in spring. This hypothesis was further supported by the statistically significantly higher concentrations of the total proteins, Zn and Fe, as well as the Fulton condition indices in the spring period.     

Assessment of the effects of the carbamazepine on the endogenous endocrine system of Daphnia magna

In the present study, the endocrine activity of the antiepileptic pharmaceutical carbamazepine (CBZ) in the crustacean Daphnia magna was assessed. To assess the hormonal activity of the drug, we exposed maternal daphnids and embryos to environmental relevant concentrations of CBZ (ranging from 10 to 200 μg/L) and to mixtures of CBZ with fenoxycarb (FEN; 1 μg/L). Chronic exposure to CBZ significantly decreased the reproductive output and the number of molts of D. magna at 200 μg/L. This compound induced the production of male offspring (12?±?1.7 %), in a non-concentration-dependent manner, acting as a weak juvenile hormone analog. Results showed that this substance, at tested concentrations, did not antagonize the juvenoid action of FEN. Further, CBZ has shown to be toxic to daphnid embryos through maternal exposure interfering with their normal gastrulation and organogenesis stages but not producing direct embryo toxicity. These findings suggest that CBZ could act as an endocrine disruptor in D. magna as it decreases the reproductive output, interferes with sex determination, and causes development abnormality in offspring. Therefore, CBZ could directly affect the population sustainability.

     

长江口南槽水域污染物迁移和分布规律

经对长江口南槽水域水质指标监测表明,在近岸带,水体中悬浮颗粒吸附态磷和各种重金属的浓度较低,而氨氮、硝氮和总溶解态磷的浓度明显偏高;在南槽主航道至九段沙水域,水体中悬浮颗粒吸附态磷和各种重金属的浓度明显增加。水体中溶解态磷的浓度很低,磷的赋存形态以悬浮颗粒吸附态磷为主,水体中重金属元素的赋存形态也以悬浮颗粒吸附态为主。落潮时的悬浮颗粒、TP、悬浮颗粒吸附态磷和重金属总浓度明显高于涨潮。水体中各种重金属总浓度之间存在显著的相关性。     

Performance of the supported copper oxide catalysts for the catalytic incineration of aromatic hydrocarbons

A fixed bed reactor was used to assess the catalytic incineration of toluene by various transition-metal oxide species supported on gamma-Al(2)O(3). CuO/gamma-Al(2)O(3) was found to be the most active of seven catalysts investigated. The CuO species, with a Cu content of 5% (wt), was hence used with four different supports (CeO(2), gamma-Al(2)O(3), TiO(2) and V(2)O(5)) in order to define the optimal combination. Results of the catalytic incineration of toluene, X-ray diffraction (XRD) analysis, oxygen-temperature programmed desorption (O(2)-TPD), toluene-temperature programmed desorption (toluene-TPD) and hydrogen-temperature programmed reduction (H(2)-TPR) showed that CuO/CeO(2) was the most active catalyst, followed by CuO/gamma-Al(2)O(3). The activity of CuO/CeO(2) with respect to the VOC molecule was observed to follow this sequence: toluen>p-xylene>benzene. The addition of water vapor or CO(2) significantly inhibited the activity of the CuO/CeO(2) and CuO/gamma-Al(2)O(3) catalysts. The inhibiting effect of both was reversible for CuO/gamma-Al(2)O(3). For CuO/CeO(2), the inhibiting effect of CO(2) was reversible and even insignificant at a higher temperature (220 degrees C), but the effect of H(2)O vapor was somewhat irreversible at lower incineration temperatures (220 degrees C). For complete oxidation of toluene, the required reaction temperature increased with gas hourly space velocity (GHSV) and toluene inlet concentration.     

Chlorophyll, carotenoids and the activity of the xanthophyll cycle

Clone spruce trees (Picea abies L. Karst.) were exposed in the Hohenheim open-top chambers to low levels of O(3) and SO(2), singly and in combination, and to simulated precipitation of two pH treatments (Seufert et al., this volume). At the end of five years of continuous exposure, needles from the 13-year-old trees were sampled and analysed for pigments content by means of HPLC (high pressure liquid chromatography). The pigment content was determined for three needle age classes. Chlorophyll a content, measured on a dry weight basis, was similar for all needle age classes in the control chambers receiving only the simulated rain treatments at pH 5.0 or 4.0, and the chamber receiving O(3) and the rain treatment at pH 4.0. Also, no differences were noted in one-year-old needles in the chambers with SO(2) and simulated precipitation at pH 4.0 and SO(2) + O(3) and simulated precipitation at pH 4.0. Reductions of approximately 10 and 35% were measured in two-year-old needles from the chambers with SO(2) and precipitation at pH 4.0, and SO(2) + O(3) and precipitation at pH 4.0. The three-year-old needles from these chambers had 40% lower chlorophyll a content compared to the control chambers. No treatment effects were seen on the molar ratios of chlorophyll b, the carotenes, lutein, neoxanthin, and the sum of carotenoids involved in the xanthophyll cycle, violaxanthin + antheraxanthin + zeaxanthin, to chlorophyll [Formula: see text]. The xanthophyll cycle, assayed in one-year-old needles under defined light conditions (520 microE m(-2) s(-1), while light) was active in all samples. Needles from the control chambers and the chambers with SO(2) and with O(3) behaved similarly and differed from the SO(2) + O(3) treated needles by a 50% higher zeaxanthin content reached under light.     

An evaluation of the green chelant EDDS to enhance the stability of hydrogen peroxide in the presence of aquifer solids

Hydrogen peroxide is a widely used in situ chemical oxidation reagent which relies on catalysts to generate the suite of reactive species that are required to aggressively remediate contaminated soils and groundwater. In the subsurface environment these catalysts are usually transition metals that are added to the injected solution, or are naturally occurring. Chelating agents are widely used to maintain an adequate dissolved transition metal concentration in near-neutral pH conditions; however, they can also be used to improve the persistence of H(2)O(2) in situations when the aquifer solids have sufficient transition metal content. Ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) have been considered to be the most effective chelants and therefore are the most widely used. While previous research efforts have focused on the chelating agent efficiency, the long-term fate of these chelants in the natural subsurface environment is a concern since both EDTA and NTA are non-readily biodegradable. The focus of this investigation was to evaluate the potential of using the environmentally friendly or green chelating agent ethylenediaminedisuccinate (EDDS) as an alternative to EDTA or NTA to suppress the catalytic activity of naturally-occurring transition metals. A series of batch reactor and column experiments were performed using five different aquifer materials and the results demonstrate that EDDS has a comparative chelating efficiency to that of EDTA. The addition of EDDS was able to reduce the H(2)O(2) decomposition rates in the presence of the aquifer materials used in this investigation by 24-97% in well-mixed batch systems, and by 20% and 38% in the column trials where H(2)O(2) was detected in the effluent.     

Denitrification in the river estuaries of the northern Baltic Sea

Estuaries have been suggested to have an important role in reducing the nitrogen load transported to the sea. We measured denitrification rates in six estuaries of the northern Baltic Sea. Four of them were river mouths in the Bothnian Bay (northern Gulf of Bothnia), and two were estuary bays, one in the Archipelago Sea (southern Gulf of Bothnia) and the other in the Gulf of Finland. Denitrification rates in the four river mouths varied between 330 and 905 micromol N m(-2) d(-1). The estuary bays at the Archipelago Sea and the Gulf of Bothnia had denitrification rates from 90 micromol N m(-2) d(-1) to 910 micromol N m(-2) d(-1) and from 230 micromol N m(-2) d(-1) to 320 micromol N m(-2) d(-1), respectively. Denitrification removed 3.6-9.0% of the total nitrogen loading in the river mouths and in the estuary bay in the Gulf of Finland, where the residence times were short. In the estuary bay with a long residence time, in the Archipelago Sea, up to 4.5% of nitrate loading and 19% of nitrogen loading were removed before entering the sea. According to our results, the sediments of the fast-flowing rivers and the estuary areas with short residence times have a limited capacity to reduce the nitrogen load to the Baltic Sea.     

Partitioning of hydrogen peroxide between the gas and liquid phases in the presence of surfactant

Gas-liquid phase partitioning is a key physical property that can predict the environmental fate of a compound between two phases. Several environmental factors have been known to affect the gas-liquid phase partitioning. We investigated the influence of surfactant on the gas-liquid phase partitioning of hydrogen peroxide (H(2)O(2)). The surfactant used was ammonium perfluorooctanoate (APFO). H(2)O(2) solution containing the surfactant was equilibrated in a closed system and gas phase H(2)O(2) concentration was measured by the peroxyoxalate chemiluminescence (PO-CL) method. Gas phase H(2)O(2) concentrations remained constant below the critical micelle concentration (CMC) and increased linearly with surfactant concentration above the CMC, which indicated that surfactant micelles influenced the gas-liquid phase partitioning of H(2)O(2). This result showed that H(2)O(2)-micelle interactions are less favorable than H(2)O(2)-H(2)O interactions. Surfactant monomers did not affect the gas-liquid phase partitioning of H(2)O(2) due to the absence of micelles. Solvent (methanol) effect was also investigated and showed that gas phase H(2)O(2) concentrations increased with the addition of solvent. This indicated the unfavorable interaction of H(2)O(2) with hydrophobic medium compared to hydrophilic one. It is consistent with the result that H(2)O(2)-micelles has a weaker interaction than H(2)O(2)-water because surfactant micelles are hydrocarbon-like organic phase rather than aqueous phase.     

Influence of the very polluted inputs of the Tinto-Odiel system on the adjacent littoral sediments of southwestern Spain: a statistical approach

A spatial and temporal analysis (period 1990-2003) of 15 sampling points distributed along the southwestern Spanish coast permits to delimitate the influence area of the extremely polluted discharges coming from the Tinto-Odiel system in the bottom sediments of the adjacent littoral area. As, Cu, Pb and Zn are the main heavy metals transported by the freshwater runoffs toward the shallow shelf and present very high negative (r < -0.7) and significant (p < 0.001) correlations with the distance to the estuarine mouth. The statistical analysis (index of geoaccumulation, Pearson correlation matrix, cluster analysis) of their concentrations in the littoral sediments located between the Guadiana and Guadalquivir mouths delimitates three zones: (a) Zone 1 (from the estuarine mouth to 6 km to the east), characterized by moderate to strongly polluted bottom sediments and main responsible of the mean annual variations of the former heavy metals in the area studied; (b) Zone 2 (from 21.2 km to the west to 29 km to the east), characterized by moderate pollution levels; and (c) Zone 3, located near the Guadiana and Guadalquivir mouths, with very low As-Cu-Pb contents and unpolluted to moderately levels of Zn due to urban sewages or the presence of local low mobility areas for this element.     

Visualisation of the complexity of EUSES

The interdependencies of parameters applied in the models of EUSES are visualised in a directed connectivity graph. The parameters (inputs, defaults, state variables, outputs) are represented by boxes (nodes) and their relations by lines (edges). The visualisation, on the one hand, clarifies the complexity of the models in EUSES and, on the other hand, creates an overview and transparency. The parameters’ relations to each other can be recognised faster, and the models can be better understood. The complexity was quantified by the number (variety), kind (substance parameter, physico-chemical parameter, concentration, other parameters), and depth (dimension) of the parameter and the number of relations (connectivity). The variety of EUSES (without the modelsSimple Treat andSimple Box whose interior structure is not documented and without the effect and risk characterisation) amounts to 466, the connectivity to 961, and the maximal dimension is 21.     

Challenge of the Future

ABSTRACT

The separation of Cr(III) from collagen in chromium-tanned leather (wet-blue) is achieved by a combination of the protein (collagen) stabilization (protective cross-linking) and a subsequent labilization of the Cr(III) species bound to the protein. During the separation collagen retains the tertiary triple helical and higher (fibril) structures. The model proposed for the protective cross-linking involves inter- rather than intramolecular bridging, that is, a supramolecular bridging. The process of chromium removal takes place in a restricted aqueous environment, and it can be characterized as semihomogeneous or semiheterogeneous.