Sediment pesticides

Soils and waters affected by emissions from smelters, power plants. Soils and waters affected by mining wastes and by-products. Some playa lake sediments. Soils and dusts derived from naturally As-enriched rocks and sediments. Waters that have leached As from As-rich rocks, soils, and sediments. Pesticides, other industrial chemicals. By-products or wastes from chemical manufacturing or other industrial processes. 

Marsh and Pond S ediments. Herbicides and pesticides are detectable ia marsh and pond sediments, but intrinsic biodegradation is usually found to be occurting. Littie work has yet been presented where the biodegradation of these compounds has been successfully stimulated by a bioremediation approach. 

Pesticide Dispersants. Modified ligaosulfates are used ia the formulatioa of pesticides, la wettable powders, suspeasioa coaceatrates, and water dispersible granules, they act as dispersants and prevent sedimentation. They also act as biaders ia the productioa of granular pesticides. Typical usage levels ia these types of products range from 2—10%. 

For many modeling purposes, Nhas been assumed to be 1 (42), resulting in a simplified equation, S = C, where is the linear distribution coefficient. This assumption usually works for hydrophobic polycycHc aromatic compounds sorbed on sediments, if the equdibrium solution concentration is <10 M (43). For many pesticides, the error introduced by the assumption of linearity depends on the deviation from linearity. 

It appears that pesticides with solubiHties greater than 10 mg/L are mainly transported in the aqueous phase (48) as a result of the interaction of solution/sediment ratio in the mnoff and the pesticide sorption coefficient. For instance, on a silt loam soil with a steep slope (>12%), >80% of atra2ine transport occurs in the aqueous phase (49). In contrast, it has been found that total metolachlor losses in mnoff from plots with medium ground slopes (2—9%) were <1% of appHed chemical (50). Of the metolachlor in the mnoff, sediment carried 20 to 46% of the total transported pesticide over the monitoring period. 

Nowel, L.H. et al. (1999) Pesticides in Stream Sediment and Aquatic Biota, CRC Press. 

I. Eeirer, M. C. Hennion and D. Barcelo, Immunosorbents coupled on-line with liquid chi omatography/atmospheric pressure chemical ionization/mass specti ometiy for the part per trillion level determination of pesticides in sediments and natural waters using low preconcenti ation volumes . Anal. Chem. 69 4508-4514 (1997). 

The results of map generation cannot be expressed effectively with the format available here. However, the State of Oregon utilized the map and matrix techniques in their nonpoint source evaluation and as a basis for designing more intensive survey approaches to assessing the impact of human activity on river quality. In addition to reflecting deposition of sediments, the methods can be applied to transport of pesticides, nutrients and trace elements since many of these substances tend to adsorb to the organic and inorganic fractions of soil. 

Hydrocarbons. In other publications the historical trend of organic pollutant concentrations, namely polychlorinated biphenys (PCBs), chlorinated pesticides DDT and metabolites DDE, DDD, and polycyclic aromatic hydrocarbons (PAHs), have been reconstructed. For this purpose the sediments of the core sampled in the Lagoon area close to the industrial district were employed (16,17). 

Weston DP, You J, Lydy MJ (2004) Distribution and toxicity of sediment-associated pesticides in agriculture-dominated water bodies of California s Central Valley. Environ Sci Technol 38(10) 2752-2759... 

Marine sediments, adjacent to a pesticide manufacturing plant in Denmark, contained methyl parathion levels of 40.6 and 44.1 pg/kg dry weight at depths of 0-3 and 4-8 cm, respectively (Kjolholt 1985). 

Belisle AA, Swineford DM. 1988. Simple, specific analysis of organophosphoms and carbamate pesticides in sediments using column extraction and gas chromatography. Environ Toxicol Chem 7 749-752. 

Glooschenko WA, Strachan WM, Sampson RC. 1976. Distribution of pesticides and polychlorinated biphenyls in water, sediments, and seston of the upper Great Eakes—1974. Pestic Monit J 10 61-67. 

Kjolholt J. 1985. Occurrence of organophosphoms compounds in polluted marine sediments near a pesticide manufacturing plant. Chemosphere 14 1763-1770. 

Environment Canada. 1999. Environment Canada, Environmental Protection Branch, Atlantic Region. March 1999. Pesticide residue in sediment and water from two watersheds in Prince Edward Island,... 

Olney CE. 1972. Transfer of pesticides through water, sediments, and aquatic life. U.S. Nat Tech Inform Serv, PB Rep. Kingston, RI University of Rhode Island. Water Resources Project A-038-RI. 

CRMs for Contaminants in Environmental Matrices For nearly two decades NIST has been involved in the development of SRMs for the determination of organic contaminants such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and chlorinated pesticides in natural environmental matrices such as fossil fuels (Hertz et al.1980 Kline et al. 1985), air and diesel particulate material (May and Wise 1984 Wise et al. 2000), coal tar (Wise et al. 1988a), sediment (Schantz et al. 1990, 1995a Wise et al. 1995), mussel tissue (Wise et al. 1991 Schantz et al. 1997a), fish oil, and whale blubber (Schantz et al. 1995b). Several papers have reviewed and summarized the development of these environmental matrix SRMs (Wise et al. 1988b Wise 1993 Wise and Schantz 1997 Wise et al. 2000). Seventeen natural matrix SRMs for the determination of organic contaminants are currently available from NIST with certified and reference concentrations primarily for PAHs, PCBs, chlorinated pesticides, polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofiirans (PCDFs) see Table 3.11. 

DE Boer J and Wells DE (1996) The 1994 QUASIMEME laboratory performance studies chlor-obiphenyls and organochlorine pesticides in fish and sediment. Mar Poll Bull 32 654-666. 

For pesticide residue immunoassays, matrices may include surface or groundwater, soil, sediment and plant or animal tissue or fluids. Aqueous samples may not require preparation prior to analysis, other than concentration. For other matrices, extractions or other cleanup steps are needed and these steps require the integration of the extracting solvent with the immunoassay. When solvent extraction is required, solvent effects on the assay are determined during assay optimization. Another option is to extract in the desired solvent, then conduct a solvent exchange into a more miscible solvent. Immunoassays perform best with water-miscible solvents when solvent concentrations are below 20%. Our experience has been that nearly every matrix requires a complete validation. Various soil types and even urine samples from different animals within a species may cause enough variation that validation in only a few samples is not sufficient. 

Pesticide immunoassays have been developed for a variety of pesticides and, more recently, GMOs, and have been used for matrices such as surface water, groundwater, runoff water, soil, sediment, crops, milk, meat, eggs, grain, urine and blood. ° Table 9 is a partial list of immunoassays for chemical pesticides developed since 1995 and includes notations on the matrices studied. A fairly comprehensive list of pesticide immunoassays developed prior to 1994 was provided by Gee et al2 ... 

The method above, however, is not suitable when one needs a precise study of the vertical distribution of pesticides. Generally, the concentration of pesticides in paddy sediment is highest at the surface. Special care is required to avoid contamination with surface soil when the sediment is collected. The sediment core should be collected in two stages. First, a pipe with a diameter greater than that of the core sampler is inserted in the sediment and then water inside the pipe is removed gently with a syringe, pipet, etc. Next, a layer of surface soil (1-3 cm) is taken with a spatula or a trowel and then subsurface soil is collected with a core sampler to the desired depth see also Figure 4. 

Special care is required to prevent contamination with surface soil when the sediment is collected to study the vertical distribution of a pesticide. The method described earlier (Section 3.1.1) is strongly recommended. 

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