Vol. 15—1961 - NorthEastern Weed Science Society

Vol. 15—1961 - NorthEastern Weed Science Society Vol. 15—1961 - NorthEastern Weed Science Society

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546. A PRELIMINARYREPORTON THE EFFECT OF SOME AQUATICHERBICIDES ON WATERQUALITyl (Abstract) by Samuel D. Faust 2, Robert J. Tucker 3, and Osman Aly4 . Ester derivatives of 2,4-dichlorophenoxy acetic acid and 2(2.4,5-trichlorophenoxy) propionic acid have proven to be successful aquatic herbicides. There are, however, several questions to be answered concerning the effect of these compounds and their commercial formulations on the quality of a potable water supply. Among these questions are the following: Are there objectionable tastes and odors imparted to the water? Do the commercial formulations effect the chlorine demand of the water supply? Do these organic compounds of phenolic origin release free phenols to the water? If so, what are the mechanisms of release of these free phenols and how long do these compounds persist? A report 1s offered, herewith, that provides preliminary answers to these questions of the effect of aquatic herbicides on water quality. Various concentrations of two granular and one liquid formulation of esters of 2,4-dichlorophenoxy acetic acid and one liquid formulation of an ester of 2(2,4,5-trichlorophenoxy} propionic acid were added to 15 liter portions of a lake water. Each herbicide was added in concentrations of'1,5, and 10 mg/l either as their acid equivalent or as their ester equivalent. Thereupon these treated portions of water and a control system were stored in five gallon carboys at room temperature. Periodically these systems were examined for threshold odor, chlorine demand, and free phenol content. ,All analyses were made in accordance with the lOth edition of "Standard Methods fbr the Examination of Water, Sewage, and Industrial Wastes", American Public Health Association, 1955. In addition, the phenols were also determined by another method described later in the report. It was found that all four aquatic herbicides imparted objectionable odors to the water at the three concentrations examined. The qualitative description of the odor was a function of the herbicide carrier in the commercial formulation. These odors were described as aromatic (kerosene or fuel oil carriers) or musty (solid clay carriers). The average threshold odor values ranged from 25 to 250 and, in general, these values remained constant in all systems for storage periods ranging from 50 to 75 days. Ipaper of the Journal Series, New Jersey Agricultural Experiment Station, Rutgers University, The State University of New Jersey, Department of Sanitation, New Brunswick, N.J. 2Assistant Professor, Dept. of Sanitation, Rutgers University 3Re s ear ch Technician, Dept. of Sanitation, Rutgers University 4Research Assistant, Dept. of Sanitation, Rutgers University

The 15 minute, 0.1 mg/l residual chlorine demand was, in general, increased by the liquid and granular herbicide formulations. When the increase in chlorine demand was expressed as percent of the control, it was found to be a function of the type of formulation, concentration of the herbicide, and period of .storage. In general, the liquid formulations produced higher chlorine demands for a given herbicide concentration than the granular formulae. In addition, a percentagewise increase in the chlorine demand was observed in the liquid formulated systems as the concentration of the herbicide was increased from 1 to 10 mg/l. The chlorine demand of the liquid carrier systems showed an increase followed by a decrease during a 74 day storage period. Neither the herbicide concentration nor length of storage appeared to affect the percentage increase of the chlorine demand produced by one of the granular formulations. In this system, the chlorine demand increased by 50 percent and persisted for 50 days in the 1, 5, and 10 mg/l herbicide systems. The second granular formulation showed an increase followed by a decrease in chlorine demand during a storage period of 50 days. Significant amounts of 2,4 dichlorophenol and 2,4,5 trichlorophenol were found in all experimental systems. It was discovered in the course of the investigation that the 4-amino antipyrine colorimetric method offered by the 10th edition of Standard Methods does not quantitatively detect para-substituted phenols. The prescribed pH conditions of 10.0-10.~ do not permit the 4-amino antipyrine-phenol complex to develop color. Thereupon, the method was modified to pH conditions of 8.0+ 0.1 where the para-halogenated phenols developed maximum color. Consequently, higher phenol concentrations were found in the herbicide treated waters than initially indicated by the unmodified method. For example, a water treated with a 1 mgjl acid equivalent concentration of an ester formulation of 2,4-D showed a 2,4 dichlorophenol concentration of 58.2 ppb after 14 days of storage by the modified method as against a 0.0 ppb phenol concentration by the unmodified method. 547. The concentration of the free phenolic contamination was found to be a function of initial herbicide dosage and the type of formulation. The free phenol concentrations imparted to the water by the liquid formulated herbicide generally increased during a storage period of 140 days. On the other hand, the phenol concentration that resulted from the granular 2,4-D formulations generally decreased during a storage period of 92 days. For any given system, the phenol concentration increased as the herbicide dosage was increased from 1 to 10 mg/l. It is suggested that there are three mechanisms responsible for the release of free phenols from the 2,4-D and 2(2,4,5}-TP herbicides. They are as follows: (1) a free phenol impurity present in the formulation as a result of the manufacturing process, (2) chemical hydrolysis of the organic esters in water, and (3) biological degradation of the ester portion of the herbicide. Several commercial formulations of the 2,4-D herbicides were found to contain trace quantities of free 2,4 dichlorophenol. Likewise there is evidence from this inves~igation

The 15 minute, 0.1 mg/l residual chlorine demand was, in general,<br />

increased by the liquid and granular herbicide formulations. When<br />

the increase in chlorine demand was expressed as percent of the<br />

control, it was found to be a function of the type of formulation,<br />

concentration of the herbicide, and period of .storage. In general,<br />

the liquid formulations produced higher chlorine demands for a given<br />

herbicide concentration than the granular formulae. In addition, a<br />

percentagewise increase in the chlorine demand was observed in the<br />

liquid formulated systems as the concentration of the herbicide was<br />

increased from 1 to 10 mg/l. The chlorine demand of the liquid carrier<br />

systems showed an increase followed by a decrease during a 74 day<br />

storage period. Neither the herbicide concentration nor length of<br />

storage appeared to affect the percentage increase of the chlorine<br />

demand produced by one of the granular formulations. In this system,<br />

the chlorine demand increased by 50 percent and persisted for 50<br />

days in the 1, 5, and 10 mg/l herbicide systems. The second granular<br />

formulation showed an increase followed by a decrease in chlorine<br />

demand during a storage period of 50 days.<br />

Significant amounts of 2,4 dichlorophenol and 2,4,5 trichlorophenol<br />

were found in all experimental systems. It was discovered in the<br />

course of the investigation that the 4-amino antipyrine colorimetric<br />

method offered by the 10th edition of Standard Methods does not<br />

quantitatively detect para-substituted phenols. The prescribed pH<br />

conditions of 10.0-10.~ do not permit the 4-amino antipyrine-phenol<br />

complex to develop color. Thereupon, the method was modified to pH<br />

conditions of 8.0+ 0.1 where the para-halogenated phenols developed<br />

maximum color. Consequently, higher phenol concentrations were found<br />

in the herbicide treated waters than initially indicated by the unmodified<br />

method. For example, a water treated with a 1 mgjl acid<br />

equivalent concentration of an ester formulation of 2,4-D showed a<br />

2,4 dichlorophenol concentration of 58.2 ppb after 14 days of storage<br />

by the modified method as against a 0.0 ppb phenol concentration by<br />

the unmodified method.<br />

547.<br />

The concentration of the free phenolic contamination was found<br />

to be a function of initial herbicide dosage and the type of formulation.<br />

The free phenol concentrations imparted to the water by the liquid<br />

formulated herbicide generally increased during a storage period of<br />

140 days. On the other hand, the phenol concentration that resulted<br />

from the granular 2,4-D formulations generally decreased during a<br />

storage period of 92 days. For any given system, the phenol concentration<br />

increased as the herbicide dosage was increased from 1<br />

to 10 mg/l.<br />

It is suggested that there are three mechanisms responsible for<br />

the release of free phenols from the 2,4-D and 2(2,4,5}-TP herbicides.<br />

They are as follows: (1) a free phenol impurity present in the<br />

formulation as a result of the manufacturing process, (2) chemical<br />

hydrolysis of the organic esters in water, and (3) biological degradation<br />

of the ester portion of the herbicide. Several commercial formulations<br />

of the 2,4-D herbicides were found to contain trace quantities of free<br />

2,4 dichlorophenol. Likewise there is evidence from this inves~igation

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