Transformation of benzothiazole in estuarine sediments

Benzothiazole (BT) is a natural and synthetic compound occurring in aquatic sediments and wastewater. The purpose of this work was to investigate BT biogeochemistry in controlled Eh/pH microcosms (CEPMs) containing estuarine sediments of different particle sizes (coarse, intermediate, fine) under oxidized and reduced conditions vs. killed controls, and tide simulation mesocosms (TSMs) containing plants and meiofauna under well-drained (oxidized), consistently saturated/flooded (reduced), and tidal (alternating oxidized/reduced) conditions. Benzothiazole was transformed into complex product mixtures under all conditions. Benzothiazole transformation rates in CEPMs were slower under reduced conditions vs. oxidized conditions in the fine- and intermediate-grain sediments, but the same in the coarse sediment. Quiescent (unstirred) CEPMs showed greatly reduced BT transformation rates in all sediments, with half-lives on the order of 2200 to >4000 h (unstirred) vs. 640 to 1000 h in the continuously stirred systems. The TSM data showed that tidal and drained systems processed BT at identical rates, far exceeding those observed in statically flooded (reduced) TSMs. Mixing was found to be a more significant variable in BT transformation rate than either Eh or sediment particle size breakdown, with constant stirring increasing observed degradation appreciably. Otherwise, BT was transformed more readily on sediments of high surface area under oxidized conditions vs. coarser sediments and those under reducing electrochemical conditions.     

Characterization of the pesticide chlordane in estuarine river sediments

Sediments are increasingly recognized as both carrier and potential source of contaminants in aquatic environments. This study investigated the characteristics and spatial distribution of total chlordane and its three most abundant compounds, including alpha-chlordane, gamma-chlordane, and trans-nonachlor, in sediments from the Cedar and Ortega rivers, Florida, USA, using geographic information system (GIS)-based kriging analyses and field measurements. Kriging analysis showed that two areas, one from the Cedar River area and the other from the northern end of the Ortega River area, were contaminated. The maximum concentrations of total chlordane, gamma-chlordane, alpha-chlordane, and trans-nonachlor in the sediments were, respectively, 101.8, 20.1, 26.3, and 19.2 microg/kg. A plot of total organic carbon (TOC)-normalized chlordane concentrations showed that effects of grain size on sediment chlordane contamination were negligible. A principal axis analysis further revealed that a linear correlation existed between alpha-chlordane and total chlordane as well as between gamma-chlordane and total chlordane, whereas no correlation existed between trans-nonachlor and total chlordane. Comparison of total chlordane concentration with Florida Sediment Assessment Guidelines showed that the Cedar River and the northern end of the Ortega River had total chlordane concentrations above the probable effect level (4.79 microg/kg), which could pose a potential risk to aquatic life.     

Spatial distribution of DDT in sediments from estuarine rivers of central Florida

Sediments may act as both a carrier for and a potential source of contaminants such as toxic organics in aquatic environments. This study investigated the spatial distribution of the pesticide DDT [1,1, 1-trichloro-2,2-bis(p-chlorophenyl)ethane] in sediments from the Cedar and Ortega Rivers located in the lower St. Johns River basin, Florida, USA, using field measurements and three-dimensional kriging analysis. High DDT concentrations were found near the junction of the Cedar and Ortega Rivers and at the north end of the Ortega River in the upper 0.5 m of the sediments, indicating that the sediment was enriched with DDT in the top layer although use of this chlorinated compound was banned in 1972. Further study revealed that the influence of sediment grain size or texture on DDT contamination was negligible in this river system and no linear correlations existed among DDT and its metabolites such as DDD [1,1-dichloro-2,2-bis(p-chlorophenyl)ethane] and DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene]. Comparison of three-dimensional distribution of DDT content to the Florida sediment quality assessment guideline or probable effect level (PEL) showed several "hot spots" in the Ortega River sediments, where DDT contents exceeded the PEL value of 4.78 microg kg(-1). Such contamination may pose a significant hazard to aquatic life.     

Weathering of lead bullets and their environmental effects at outdoor shooting ranges

Lead contamination at shooting range soils is of great environmental concern. This study focused on weathering of lead bullets and its effect on the environment at five outdoor shooting ranges in Florida, USA. Soil, plant, and water samples were collected from the ranges and analyzed for total Pb and/or toxicity characteristic leaching procedure (TCLP) Pb. Selected bullet and berm soil samples were mineralogically analyzed with X-ray diffraction and scanning electron microscopy. Hydrocerussite [Pb3(CO3)2(OH)2] was found in both the weathered crusts and berm soils in the shooting ranges with alkaline soil pH. For those shooting ranges with acidic soil pH, hydrocerussite, cerussite (PbCO3), and small amount of massicot (PbO) were predominantly present in the weathered crusts, but no lead carbonate mineral was found in the soils. However, hydroxypyromorphite [(Pb10(PO4)6(OH)2] was formed in a P-rich acidic soil, indicating that hydroxypyromorphite can be a stable mineral in P-rich shooting range soil. Total Pb and TCLP Pb in the soils from all five shooting ranges were significantly elevated with the highest total Pb concentration of 1.27 to 4.84% (w/w) in berm soils. Lead concentrations in most sampled soils exceeded the USEPA's critical level of 400 mg Pb kg(-1) soil. Lead was not detected in subsurface soils in most ranges except for one, where elevated Pb up to 522 mg kg(-1) was observed in the subsurface, possibly due to enhanced solubilization of organic Pb complexes at alkaline soil pH. Elevated total Pb concentrations in bermudagrass [Cynodon dactylon (L.) Pers.] (up to 806 mg kg(-1) in the aboveground parts) and in surface water (up to 289 microg L(-1)) were observed in some ranges. Ranges with high P content or high cation exchange capacity showed lower Pb mobility. Our research clearly demonstrates the importance of properly managing shooting ranges to minimize adverse effects of Pb on the environment.     

Combined chemical and biological oxidation of penicillin formulation effluent

Antibiotic formulation effluent is well known for its important contribution to environmental pollution due to its fluctuating and recalcitrant nature. In the present study, the chemical treatability of penicillin formulation effluent (average filtered COD(o)=830 mg/l; average soluble COD(o)=615 mg/l; pH(o)=6.9) bearing the active substances penicillin Amoxicillin Trihydrate (C(16)H(19)N(3)O(5)S.3H(2)O) and the beta-lactamase inhibitor Potassium Clavulanate (C(8)H(8)KNO(5)) has been investigated. For this purpose, the penicillin formulation effluent was subjected to ozonation (applied ozone dose=2500 mg/(lxh)) at varying pH (2.5-12.0) and O(3)+H(2)O(2) (perozonation) at different initial H(2)O(2) concentrations (=2-40 mM) and pH 10.5. According to the experimental results, the overall Chemical Oxygen Demand (COD) removal efficiency varied between 10 and 56% for ozonation and 30% (no H(2)O(2)) and 83% (20 mM H(2)O(2)) for the O(3)+H(2)O(2) process. The addition of H(2)O(2) improved the COD removal rates considerably even at the lowest studied H(2)O(2) concentration. An optimum H(2)O(2) concentration of 20 mM existed at which the highest COD removal efficiency and abatement kinetics were obtained. The ozone absorption rate ranged between 53% (ozonation) and 68% (perozonation). An ozone input of 800 mg/l in 20 min was sufficient to achieve the highest BOD(5)/COD (biodegradability) ratio (=0.45) and BOD(5) value (109 mg/l) for the pre-treated penicillin formulation effluent. After the establishment of optimum ozonation and perozonation conditions, mixtures of synthetic domestic wastewater+raw, ozonated and perozonated penicillin formulation effluent were subjected to biological activated sludge treatment at a food-to-microorganisms (F/M) ratio of 0.23 mg COD/(mg MLSSxd), using a consortium of acclimated microorganisms. COD removal efficiencies of the activated sludge process were 71, 81 and 72% for pharmaceutical wastewater containing synthetic domestic wastewater mixed with either raw, ozonated or perozonated formulation effluent, respectively. The ultimate COD value obtained after 24-h biotreatment of the synthetic domestic wastewater+pre-ozonated formulation effluent mixture was around 100 mg/l instead of 180 mg/l which was the final COD obtained for the wastewater mixture containing raw formulation effluent, indicating that pre-ozonation at least partially removed the non-biodegradable COD fraction of the formulation effluent.     

Combinatory chemical and biological approaches to investigate metal elements in agricultural runoff water

As part of a project studying the interactions between farming practices, soil erosion processes, and fate of agricultural pollutants into runoff waters, we conducted a pilot study to investigate the relationship between metal contents and metallothionein-2A (MT-2A) as a bioindicator of metal exposure. Runoff water samples were collected between May and November 1999 at the point of outlet of an elementary watershed located in the Paris basin. Selected metals (Al, As, Cd, Cr, Cu, Pb, Hg, Ni, and Zn) were analyzed using conventional techniques. In parallel, human T cells were exposed to water samples for 6 and 18 h and then cell viability and MT-2A gene expression were measured. Results show that among the 10 water samples tested, Al and Zn predominate (highest values = 4.9 and 2.6 microM, respectively), while other metals were below the microM level. Five out of 10 samples induced MT-2A gene expression (30-80% increase at 18 h) as compared with the control. When comparing MT-2A induction profile with metals contents, no obvious correlation was found, suggesting that additional components or parameters are involved. Finally, there was an apparent inverse relationship between Ca concentration and MT-2A gene induction. Although still preliminary, in the absence of longer monitoring, this study shows that MT-2A gene expression is a useful tool to complement chemical analysis in assessing metal elements in water. These combinatory approaches will be pursued and integrated in an ongoing watershed field research project.     

Comparison of trace metal contents of sediments and mussels collected within and outside Tolo Harbour,Hong Kong

Sediments collected from Tap Mun (within Tolo Harbour) and Yim Tin Tsai (outside Tolo Harbour) were extracted sequentially and the copper, cadmium, and chromium contents were determined. Total contents of copper, cadmium, chromium, and arsenic were also detected by acid digestion. The level of heavy metal extracted was higher in sequential extraction (which extracted all forms of metal ions) than total acid digestion. Among the four heavy metals studied, only copper showed a significantly higher (P<0.001) level in samples collected from Yim Tin Tsai (16.10 mg/kg) than that from Tap Mun (3.19 mg/kg). Such a difference in copper level is mainly attributed to the significantly higher (P<0.05) levels of copper in the organic, carbonate, and sulfide forms, whereas there was no significant difference (P>0.05) in the exchangeable and sorbed forms. Green-lipped mussel (Perna viridis) samples collected from the two sites were dissected into seven parts (gill, byssus, siphon, shell, digestive gland, soft tissue, and adductor muscle) and the concentrations of copper, cadmium, chromium, and arsenic were measured. The highest concentration of copper was obtained in the byssus. A higher concentration of copper was also noted in the mussels collected from Yim Tin Tsai than those collected from Tap Mun. No specific trend was revealed for the other metals tested. Chromium and arsenic concentrations were found to be independent of the body size of the mussels. Copper had a lower concentration in larger mussels and cadmium level was found to decrease with size. In addition, the mussels collected from Tap Mun were much larger than those collected from Yim Tin Tsai.     

Long-term biosolids application effects on metal concentrations in soil and bermudagrass forage

The long-term application of biosolids that periodically contained elevated metal concentrations has raised questions about potential effects on animal health. To address these concerns, we determined metal concentrations (As, Cd, Cu, Pb, Hg, Mo, Ni, Se, and Zn) in both soil and bermudagrass [Cynodon dactylon (L.) Pers.] forage from 10 fields in the following categories of biosolids application: six or more years (>6YR), less than six years (<6YR), and no applications (NS). Soil metal concentrations in all groups were similar to values reported for mineral soils in Georgia, and well below USEPA cumulative limits. Average metal concentrations in the forage were below the maximum tolerable level (MTL) for beef cattle, although two biosolids-amended fields in the >6YR group produced forage that was at or near the MTL for Cd and Mo, and one field in the <6YR group produced forage above the MTL for Cd. The Cu to Mo ratios in forage decreased with increasing time of sludge application, with the average in the >6YR group at a proposed 5:1 Cu to Mo ratio limit to protect ruminant health. Sulfur concentrations in the forage from all three groups was near the MTL of 4 g kg(-1). The study indicated that toxic levels of metals have not accumulated in the soils due to long-term biosolids application. Overall forage quality from the biosolids-amended fields was similar to that of commercially fertilized fields; however, due to the relatively high S and potential for a low Cu to Mo ratio, Cu supplements should be used to ensure ruminant health.     

Managing the adverse thermal effects of urban development in a densely populated Chinese city

Guangzhou city in South China has experienced an accelerated urban development since the 1980s. This paper examines the impact of the urban development on urban heat islands through a historical analysis of urban-rural air temperature differences. Remote sensing techniques were applied to derive information on land use/cover and land surface temperatures and to assess the thermal response patterns of land cover types. The results revealed an overriding importance of urban land cover expansion in the changes in heat island intensity and surface temperature patterns. Urban development was also related to a continual air temperature increase in the 1980s and 1990s. The combined use of satellite-derived vegetation and land cover distributions with land surface temperature maps provides a potential useful tool for many planning applications. The city's greening campaigns and landscaping designs should consider the different cooling effects of forest, shrubs and grassy lawns for temperature control and should plant more tall trees.     

Evaluation of nitrogen retention and microbial populations in poultry litter treated with chemical, biological or adsorbent amendments

Poultry litter is a valuable nutrient source for crop production. Successful management to reduce ammonia and its harmful side-effects on poultry and the environment can be aided by the use of litter amendments. In this study, three acidifiers, two biological treatments, one chemical urease inhibitor and two adsorber amendments were added to poultry litter. Chemical, physical and microbiological properties of the litters were assessed at the beginning and the end of the experiment. Application of litter amendments consistently reduced organic N loss (0-15%) as compared to unamended litter (20%). Acidifiers reduced nitrogen loss through both chemical and microbiological processes. Adsorbent amendments (water treatment residuals and chitosan) reduced nitrogen loss and concentrations of ammonia-producing bacteria and fungi. The use of efficient, cost-effective litter amendments to maximum agronomic, environmental and financial benefits is essential for the future of sustainable poultry production.