OUTLIER DETECTION IN TOTAL PHOSPHORUS CONCENTRATION DATA FROM SOUTH FLORIDA RAINFALL1

ABSTRACT: Atmospheric deposition can be a significant source of phosphorus to South Florida's aquatic system. Deposition samples are often contaminated to varying degrees by bird droppings or other foreign materials. This study attempted to use statistical and other methods to detect and remove the outliers in the rain-borne total phosphorus concentration data. Some outliers in the data were identified using field notes derived from visual inspection of the samples. Outlier detection statistics based on a simple linear regression were then used for additional data screening. As a result of these analyses, about 35 percent of the observed values were identified as outlying data which needed to be removed prior to further data analyses. Based on detected outliers in the data from 15 monitoring sites, a lumped cutoff value of 130 4mUg/L was determined. This lumped cutoff value may be useful for further quality control and analyses of the data from the region.     

EFFECT OF FLOW VELOCITY ON SEDIMENT OXYGEN DEMAND: COMPARISON OF THEORY AND EXPERIMENTS1

ABSTRACT: Theoretical equations that establish the relationship between sediment oxygen demand (SOD) in a lake and the flow velocity and dissolved oxygen concentration in the bulk water already exist. These theoretical equations for oxygen consumption in the sediment express biological consumption with Michaelis-Menten kinetics, and chemical consumption by a first order reaction. Data from laboratory experiments that were conducted to validate the theoretical equations also exist. These experiments were performed in a laboratory channel with well defined flow characteristics for three types of sediments. Herein, the theoretical equations are used to model the experimental data for the three types of sediments. The values used for the parameters in the theoretical equations are determined by iteration until a best fit is obtained for the relationship of SOD to flow velocity from both the theoretical model and experimental data. The goodness of fit is measured by the standard error of prediction and the regression coefficient.     

Outlier detection in phosphorus dry deposition rates measured in South Florida

Dry atmospheric deposition contributes a significant amount of phosphorus to the Everglades of South Florida. Measurement of this deposition is problematic, because samples often are contaminated to varying degrees by bird droppings and other foreign materials. This study attempted to detect and remove the outliers in phosphorus (P) flux rates measured from dry deposition samples. Visual inspection of the samples, recorded in field notes, found that 30.1% of the samples contained animal droppings and frogs. Some of the samples with droppings and frogs (2.3%) had P values greater than 884 μg P m⁻² d⁻¹ (a value twice the standard deviation of the raw data mean), and were removed from further analysis. Outlier detection statistics based on a linear regression were then used for additional data screening. Eight stations in the network of 19 were removed because high contamination precluded the use of the regression model. Of the remaining samples, 15.7% were identified through the regression procedure as contaminated and were removed. The 11 station mean for P dry deposition was 85.8±79.0 μg P m⁻² d⁻¹, prior to the regression analysis, and 74.8±75.1 μg P m⁻² d⁻¹ after removal.     

Biotransformation of 17α-methyltestosterone in sediment under different electron acceptor conditions

17α-Methyltestosterone (MT), an anabolic androgenic steroid, is used widely in inducing an all male population in aquaculture farming of fish, such as Nile tilapia (Oreochromis niloticus). Current understanding of the occurrence and fate of MT in the sediments and the surrounding areas of the aquaculture ponds are very limited. Bioassay tests showed that MT was biotransformed under aerobic and sulfate-reducing conditions with a half-life of 3.8 d and 5.3 d, respectively, with complete disappearance of androgenic activity. However, under methanogenic condition, MT was found to biotransform but the androgenic activity continued to persist even after 45 d of incubation. In contrast, MT was found to transform slowly under iron(III)-reducing condition and was hardly transformed under nitrate-reducing condition. A possible reason for the lack of transformation of MT under nitrate-reducing condition is the presence of the methyl group at the C-17 position. The results of this study suggest that MT and its degradation products with androgenic activity may potentially accumulate in the sediments of fish farming ponds under iron(III)-reducing, nitrate-reducing and methanogenic conditions.     

Occurrence and distribution of sediment-associated insecticides in urban waterways in the Pearl River Delta, China

Sediment-associated pesticides, including organochlorine (OCP), organophosphate (OP), and pyrethroid insecticides, were analyzed in urban waterways in three cities (Guangzhou, Dongguan, and Shenzhen) in the Pearl River Delta (PRD), China. The OCPs represented 27.2% of the detectable insecticides in sediment, and chlordanes, DDTs, and endosulfans were the most frequently detected OCPs. The currently used insecticide chlorpyrifos was the only OP detected above the reporting limit (RL), with concentrations ranging from <RL to 100 ng g⁻¹ dry weight (dw). Additionally, pyrethroids were detected in all sediments with the sum pyrethroid concentrations ranging from 4.26 to 384 ng g⁻¹ dw and this represented 64.9% of the sum insecticide concentration. Despite their widespread use, no studies have been conducted investigating the occurrence and distribution of pyrethroids in China. As the first report of pyrethroids in urban waterways in China, the current study found cypermethrin was the most abundant insecticide detected in the PRD at concentrations ranging from 1.44 to 219 ng g⁻¹ dw. Spatially, sediment from more populous and urbanized areas (Shenzhen and Tianhe district in Guangzhou) had higher insecticide residues than less populous agricultural areas. In the more modernized city of Shenzhen, the OCPs were seldom detected, whereas more diverse patterns of pyrethroids were observed. Potential sources of these insecticides, especially the frequently detected pyrethroids, were most likely from pest control during urban landscaping maintenance and from abatement programs targeting mosquitoes and ants. Results suggested that a shift in application pattern and elevated urbanization increased accumulation of currently used insecticides like pyrethroids in sediment, and made them the predominate insecticides in the PRD urban waterways.     

Occurrence and treatment of arsenic in groundwater and soil in northern Mexico and southwestern USA

This review focuses on the occurrence and treatment of arsenic (As) in the arid region of northern Mexico (states of Chihuahua and Coahuila) and bordering states of the southwestern US (New Mexico, Arizona, and Texas), an area known for having high As concentrations. Information assembled and assessed includes the content and probable source of As in water, soil, and sediments and treatment methods that have been applied in the area. High As concentrations were found mainly in groundwater, their source being mostly from natural origin related to volcanic processes with significant anthropogenic contributions near mining and smelting of ores containing arsenic. The affinity of As for solid phases in alkaline conditions common to arid areas precludes it from being present in surface waters, accumulating instead in sediments and shifting its threat to its potential remobilization in reservoir sediments and irrigation waterways. Factors such as oxidation and pH that affect the mobility of As in the subsurface environment are mentioned. Independent of socio-demographic variables, nutritional status, and levels of blood lead, cognitive development in children is being affected when exposed to As. Treatments known to effectively reduce As content to safe drinking water levels as well as those that are capable of reducing As content in soils are discussed. Besides conventional methods, emergent technologies, such as phytoremediation, offer a viable solution to As contamination in drinking water.     

Toxicity and metabolism of copper pyrithione and its degradation product, 2,2'-dipyridyldisulfide in a marine polychaete

We conducted acute toxicity tests and sediment toxicity tests for copper pyrithione (CuPT) and a metal pyrithione degradation product, 2,2′-dipyridyldisulfide [(PS)₂], using a marine polychaete Perinereis nuntia. The acute toxicity tests yielded 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 0.06 mg L⁻¹ and 7.9 mg L⁻¹, respectively. Sediment toxicity tests resulted in 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 1.1 mg kg⁻¹ dry wt. and 14 mg kg⁻¹ dry wt., respectively. In addition to mortality, sediment avoidance behavior and decreases in animal growth rate were observed; growth rate was the most susceptible endpoint in the sediment toxicity tests of both toxicants. Thus, we propose lowest observed effect concentrations of 0.3 mg kg⁻¹ dry wt. and 0.2 mg kg⁻¹ dry wt. for CuPT and (PS)₂, respectively, and no observed effect concentrations of 0.1 mg kg⁻¹ dry wt. for both CuPT and (PS)₂. The difference in the toxicity values between CuPT and (PS)₂ observed in the acute toxicity test was greater than the difference in these values in the sediment toxicity test, and we attribute this to (PS)₂ being more hydrophilic than CuPT. In addition to the toxicity tests, we analyzed conjugation activity of several polychaete enzymes to the toxicants and marked activity of palmitoyl coenzyme-A:biocides acyltransferase and UDP-glucuronosyl transferase was observed.     

Vertical fluxes of aromatic and aliphatic hydrocarbons in the Northwestern Mediterranean Sea

Aliphatic and aromatic hydrocarbon fluxes were measured in time series sediment trap samples at 200 m and at 1000 m depths in the open Northwestern Mediterranean Sea, from December 2000 to July 2002. Averaged fluxes of n-alkanes, UCM and T-PAH₃₅ were 2.96 ± 2.60 μg m⁻² d⁻¹, 64 ± 60 μg m⁻² d⁻¹ and 0.68 ± 0.59 μg m⁻² d⁻¹, respectively. Molecular compositions of both hydrocarbon classes showed a contamination in petrogenic hydrocarbons well above the background levels of such an open site, whereas pyrolytic hydrocarbons stand in the range of other open Mediterranean locations. Fluxes displayed ample interannual and seasonal variabilities, mainly related to mass flux variation while concentration evolutions trigger secondary changes in pollutant fluxes. High lithogenic flux events exported particles with a larger pollutant load than biogenic particles formed during the spring bloom and during the summer. Sinking hydrocarbons were efficiently transported from 200 m to 1000 m.     

2,4,6-Trinitrotoluene mineralization and bacterial production rates of natural microbial assemblages from coastal sediments

The nitrogenous energetic constituent, 2,4,6-Trinitrotoluene (TNT), is widely reported to be resistant to bacterial mineralization (conversion to CO₂); however, these studies primarily involve bacterial isolates from freshwater where bacterial production is typically limited by phosphorus. This study involved six surveys of coastal waters adjacent to three biome types: temperate broadleaf, northern coniferous, and tropical. Capacity to catabolize and mineralize TNT ring carbon to CO₂ was a common feature of natural sediment assemblages from these coastal environments (ranging to 270+/−38 μg C kg⁻¹ d⁻¹). More importantly, these mineralization rates comprised a significant proportion of total heterotrophic production. The finding that most natural assemblages surveyed from these ecosystems can mineralize TNT ring carbon to CO₂ is consistent with recent reports that assemblage components can incorporate TNT ring carbon into bacterial biomass. These data counter the widely held contention that TNT is recalcitrant to bacterial catabolism of the ring carbon in natural environments.     

Seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk from a high altitude pasture in the Italian Alps

The seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk was studied in a high altitude pasture in the Alps (1900 m a.s.l.). PCB contamination in vegetation shows a concentration peak in June, which is mainly interpreted as the consequence of a temporary PCB enrichment of the air layer above the ground due to net emission fluxes from the soil. A three compartment dynamic model was developed to test this hypothesis. The North/South enrichment factor in the vegetation was 1.5-1.6 for penta- and hexa-substituted congeners and 1.7 for hepta- and octa-PCBs, according to the effect of temperature on compounds having higher K_oa values. Milk concentrations followed the vegetation seasonal trend. The congener abundance in milk is in agreement with the biotransformation susceptibility, absorption efficiency and residence time of the different congeners in dairy cows.